Bisthiocarbamic acid esters and herbicidal use thereof

ABSTRACT

New diurethanes having a herbicidal action, the urethane radicals being attached to a phenyl radical in meta position and at least one of the urethane radicals containing sulfur; herbicides containing these compounds as active ingredients; processes for the preparation of these compounds; and processes for controlling the growth of unwanted plants with these compounds.

The present invention relates to new and valuable sulfurous diurethanes having an excellent herbicidal action, herbicides containing these compounds, and processes for controlling the growth of unwanted plants with these compounds.

It is known to use methyl-N-(3-(N'-(3'-methylphenyl)-carbamoyloxy)-phenyl)-carbamate, ethyl-N-(N'-phenylcarbamoyloxy)-phenyl-carbamate, methyl-N-(3-N'-methyl-N'-phenylcarbamoyloxy)-phenyl-carbamate (German Printed Application DAS No. 1,567,151) and 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide (German Printed Application DAS No. 1,542,836) as herbicides.

We have now found that the new diurethanes of the formula ##STR1## where Z denotes the radical ##STR2## and Y denotes the radical ##STR3## Z always being different from Y and R¹ and R² being identical or different and each denoting hydrogen, alkyl (e.g., methyl, ethyl, isopropyl), alkoxyalkyl (e.g., methoxymethyl, 2-methoxyethyl), alkoxycarbonylalkyl (e.g., methoxycarbonylmethyl), haloalkyl (e.g., chloromethyl), unsubstituted benzyl, and benzyl substituted by alkyl or halogen, R³ and R⁴ being identical or different and each denoting unsubstituted alkyl, alkyl substituted by halogen, alkoxy, alkoxycarbonyl or substituted or unsubstituted aryl (e.g., methyl, ethyl, 2-chloroethyl, 2-methoxyethyl, methoxycarbonylmethyl, benzyl, isopropyl, n-propyl, 4-chlorobenzyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2,4-dichlorobenzyl, 2-ethylhexyl, n-decyl, 2-phenylethyl), unsubstituted or halogen-substituted alkenyl (e.g., allyl, 2-chloropropen-(1)-yl-(3), buten-(1)-yl-(3), 2,3-dichloroallyl, 3,3-dichloro-2-methylallyl), unsubstituted or halogen- or alkoxy-substituted alkynyl (e.g., propargyl, butyn-(1)-yl-(3), 1-chlorobutyn-(2)-yl-(4)), unsubstituted or alkyl-substituted cycloalkyl (e.g., cyclopentyl, cyclohexyl, 3-methylcyclohexyl, 2,6-dimethylcyclohexyl, cycloheptyl, 4-tert-butylcyclohexyl, cyclooctyl, cyclododecyl, 3,5-dimethylcyclohexyl), bicycloalkyl (e.g., norbornyl), tricycloalkyl (e.g., tricyclo-(4,3,1²,5,0¹,6)-decyl), phenyl with a fused ring system (e.g., naphthyl, indyl), phenyl or mono- or polysubstituted phenyl with the substituents alkyl, haloalkyl, alkoxyalkyl, alkoxycarbonylalkyl, cycloalkyl, halogen, alkoxy, haloalkoxy, alkoxycarbonylalkoxy, nitro, amino, aryl, aryloxy, thiocyanato, cyano, ##STR4## (e.g., phenyl, 4-fluorophenyl, 2-methoxyphenyl, 3-methylphenyl, 2-fluorophenyl, 3-methyl-5-isopropylphenyl, 3-ethylphenyl, 3-chlorophenyl, 2,4,6-trimethylphenyl, 3-fluorophenyl, 3-chloro-4-fluorophenyl, 3,4-dimethylphenyl, 3-trifluoromethylphenyl, 4-methylphenyl, 3,4-difluorophenyl, 3-chloro-4-methylphenyl, 3-bromophenyl, 4-iodophenyl, 4-chlorophenyl, 2-chlorophenyl, 3-N,N-dimethylaminophenyl, 2-chloro-4-fluorophenyl, 3-isopropylphenyl, 4-ethylphenyl, 3-methoxycarbonylaminophenyl, 4-ethoxyphenyl, 2-methylphenyl, 3-methoxyphenyl, 4-cyanophenyl, 2,6-dimethylphenyl, 2,4-dichlorophenyl, 3-methyl-4-chlorophenyl, 2-trifluoromethylphenyl, 2,4-dibromophenyl, 4-trifluoromethylphenyl, 4-methoxyphenyl, 3-(1'-ethoxycarbonylethoxy)-phenyl, 2,3,6-trimethylphenyl, 3-tert.-butylphenyl, 3-trifluoromethoxyphenyl, 3-α,α,β,β-tertrafluoroethoxyphenyl, 3,5-dichlorophenyl, 2-methyl-6-ethylphenyl, 2,3-dimethylphenyl, 2-methyl-4-chlorophenyl, 2,4,5-trichlorophenyl, 2,3,6-trichlorophenyl, p-chlorophenoxyphenyl), R⁵ and R⁶ being identical or different and each denoting hydrogen, unsubstituted aryl or mono- or polysubstituted aryl, or one of the two substituents having the meanings given for R¹, and A, B, D and E being identical or different and each denoting oxygen or sulfur (with the proviso that one of the radicals always denotes sulfur), X denotes hydrogen, alkyl (e.g., methyl), haloalkyl (e.g., trifluoromethyl), alkoxy (e.g., methoxy), halogen (e.g., fluoro, chloro, bromo or iodo), nitro or amino, and n denotes one of the integers 1,2,3 and 4, have a good herbicidal action on numerous important unwanted plants and are also excellently tolerated by many crop plants. These effects are better than those achieved by prior art active ingredients.

The new compounds may for instance be prepared by the following methods, the radicals A,B,D,E,R¹,R²,R³,R⁴ and X and n having the above meanings. Where mention is made in the following of urethanes and chloroformic acid esters, these two terms are also intended to cover thiono-, thio- and dithiourethanes and chloroformic acid thionoesters, chloroformic acid thioesters and chloroformic acid dithioesters. ##STR5##

The interrelationships between the starting compounds will be readily apparent from this reaction scheme. It will also be clear that the one of the other route may be more advantageous, depending on the nature of the substituents A,B,D,E,R¹,R²,R³,R⁴ and X, and on the availability of the reactants. The reaction of F to H is preferred.

Starting from prior art m-nitranilines (A), m-nitrophenyliso(thio)cyanates (B) may be produced (W. Siefken, J. Liebigs Annalen der Chemie, 562, 75 et seq., 1949), which in turn smoothly react with the components R³ -BH to give nitro(thio)urethanes (C) (S. Petersen, Methoden der Organ. Chemie, VIII, 131, Georg Thieme-Verlag, Stuttgart, 4th edition, 1952), which are, however, also accessible direct from m-nitranilines (A) with chloroformic acid esters (R³ --B--CA--Cl) (German Laid-Open Application DOS No. 1,643,763), or with carbon disulfide or carbonyl sulfide, base and alkylating agent (Methoden der Organ. Chemie, IX, 831 et seq., Georg Thieme-Verlag, Stuttgart, 4th edition, 1955). Subsequent reaction gives the amino compounds (F; R² =H) (S. Schroter, Methoden der Organ. Chemie, XI/1, 360 et seq., Georg Thieme-Verlag, Stuttgart, 4th edition, 1957), which are reacted direct, or after conversion into the product monosubstituted on the amino nitrogen (F; R² =H) (Methoden der Organ. Chemie, XI/1, 24 et seq., Georg Thieme-Verlag, Stuttgart, 4th edition, 1957), with chloroformic acid esters (R.sup. 4 D--CE--Cl) (German Laid-Open Application DOS No. 1,643,763) or with carbon disulfide or carbonyl sulfide, base and alkylating agent (Methoden der Organ. Chemie, IX, 831 et seq., Georg Thieme-Verlag Stuttgart, 4th edition, 1955) to give the desired diurethanes (H). The aminourethanes (F) may also be obtained by reaction of m-phenylenediamines (D) with chloroformic acid esters. A further synthesis route is the reaction of aryl-1,3-diiso(thio)cyanates (E) with only one mole of component R³ --BH; this reaction gives the iso(thio)cyanatourethanes (G). (J. A. Parker, J. J. Thomas and C. L. Zeise, J. Org. Chem., 22, 594-596, 1957), which are also obtainable by (thio)phosgenation of aminourethanes (F) (German Laid-Open Application DOS No. 1,914,270, p. 5, Ex. 8). Subsequent reaction with the component R⁴ DH gives the desired end products. It should be noted that the --CABR³ and --CEDR⁴ groupings may be in any order.

The preferred synthesis steps are described in more detail below:

(a) The 3-nitrophenyliso(thio)cyanates (B) are reacted with or without a catalyst conventionally used for iso(thio)cyanate reactions, e.g., tertiary amines (triethylamine, 1,4-diazabicyclo-(2,2,2)-octane), nitrogenous heterocycles (pyridine, 1,2-dimethylimidazole) or organic tin compounds (dibutyl tin diacetate, dimethyl tin dichloride) if desired in a solvent inert under the reaction conditions, e.g., hydrocarbons (ligroin, gasoline, toluene, pentane, cyclohexane), halohydrocarbons (methylene chloride, chloroform, dichloroethane, chlorobenzene, o-, m- and p-dichlorobenzene), nitrohydrocarbons (nitrobenzene, nitromethane), nitriles (acetonitrile, butyronitrile, benzonitrile), ethers (diethyl ether, tetrahydrofuran, dioxane), esters (ethyl acetate, methyl propionate), ketones (acetone, methyl ethyl ketone) and amides (dimethylformamide, formamide) (German Laid-Open Application DOS No. 1,568,138) at from 0° to 150° C., preferably from 40° to 100° C.

(b) 3-nitranilines (A) are reacted with chloroformic acid esters in a suitable solvent, e.g. water, alcohols (methanol, ethanol, isopropanol), or as under (a), with the aid of a conventional acid binder, e.g., alkali metal hydroxides, carbonates, bicarbonates, alkaline earth metal oxides, hydroxides, carbonates, bicarbonates and tertiary organic bases (e.g., triethylamine, pyridine, N,N-dimethylaniline, N,N-dimethylcyclohexylamine, quinoline, tributylamine), at from -20° to +150° C., preferably from +20° to 80° C.

(c) Nitrourethanes (C) may be reduced by a prior art process, e.g., catalytic hydrogenation, a metal-acid combination such as iron-acid, or a metal-alcohol combination such as zinc dust-aqueous alcohol or iron-aqueous alcohol.

(d) For the reaction of m-phenylenediamines (D), conditions comparable to those for (b) apply; it may be advantageous to employ an excess m-phenylenediamine.

(e) Aminourethanes (F) are reacted with chloroformic acid esters analogously to (b); the solution obtained for instance by catalytic hydrogenation of nitrourethanes (C) may also be used direct without further purification.

The following examples are intended to illustrate the production of the new diurethanes and their precursors.

I. Nitrourethanes EXAMPLE A

While stirring and at 20° to 25° C., a mixture of 85 parts by weight of 3-nitrophenyl isocyanate and 43 parts by weight of absolute toluene was metered into a solution of 64.3 parts by weight of 4-chlorophenol and 3 parts by weight of triethylamine in 430 parts by weight of absolute toluene.

To complete the reaction, the mixture was stirred for 1 hour at room temperature. After cooling to 0° C., the reaction product was suction filtered; m.p.: 137°-138° C.

The compound has the following structural formula: ##STR6##

EXAMPLE B

87 parts by weight of sodium bicarbonate is added to 138 parts by weight of m-nitraniline in 500 parts by weight of tetrahydrofuran (THF). At room temperature and while stirring, 120 parts by weight of chloroformic acid thiomethyl ester is dripped in, the mixture is stirred for 16 hours at room temperature and then filtered, the solvent is distilled off in a rotary evaporator, and the oil which is obtained is stirred into toluene. The crystals which separate out are suction filtered and dried; m.p.: 137°-138° C.

The compound has the following structural formula: ##STR7##

EXAMPLE C

17.4 parts by weight of sodium bicarbonate is added to 26 parts by weight of 3-nitro-N-methylaniline in 320 parts by weight of ethyl acetate. While stirring, 33 parts by weight of chloroformic acid m-tolyl ester is slowly added, the mixture is stirred for 20 hours at room temperature and filtered, the solvent is removed in vacuo, and the residue is recrystallized from toluene/cyclohexane.

The compound has the following structural formula: ##STR8##

The following nitrourethanes (C) may be prepared analogously:

    __________________________________________________________________________      ##STR9##                                                                      A B X    R.sup.1                                                                              R.sup.3            m.p.° C.                              __________________________________________________________________________     S O H    H     methyl                                                          O O H    H     4-fluorophenyl     166-167                                      O O H    H     2,4-dichlorophenyl 150-151                                      O O H    H     methyl             153-155                                      O O 6-CH.sub.3                                                                          H     methyl             132-133                                      O O H    benzyl                                                                               4-chlorophenyl                                                  O O H    H     phenyl             123-125                                      O O H    H     3-methoxyphenyl                                                 O O H    CH.sub.3                                                                             phenyl             69-70                                        O O H    H     2-fluorophenyl     145-146                                      O O 6-F  H     phenyl             138-140                                      O O H    H     3-bromophenyl      130-131                                      O O H    CH.sub.3 OCH.sub.2                                                                   3-methylphenyl                                                  O O H    H     3,4-dimethylphenyl 130-131                                      O O 5-CF.sub.3                                                                          H     methyl             86-87                                        O O H    H     4-methoxyphenyl    132-133                                      O O 6-CH.sub.3                                                                          H     ethyl              131-133                                      O O H    H     3-fluorophenyl     128-130                                      O O H    H     ethyl              64-66                                        O O 2-CH.sub.3                                                                          H     phenyl             112-114                                      O O H    H     2-chloro-4-fluoro-                                                             phenyl             146-147                                      O O H    H     2-chlorophenyl     136-138                                      O O 4,6-F.sub.2                                                                         H     methyl                                                          O O H    C.sub.2 H.sub.5                                                                      4-cyanophenyl                                                   O O 4-CH.sub.3                                                                          H     methyl             114-117                                      O O H    H     3-trifluoromethyl- 119-120                                                     phenyl                                                          O O 2,5-Cl.sub.2                                                                        CH.sub.3                                                                             2-methoxyethyl                                                  O O H    H     4-trifluoromethyl-                                                             phenyl                                                          O O H    CH.sub.3                                                                             cyclododecyl                                                    O O H    H     4-ethylphenyl      86-88                                        O O 4-Cl H     phenyl             125-127                                      O O H    H     3-chloro-4-fluoro-                                                             phenyl                                                          O O 6-CH.sub.3                                                                          4-methyl                                                                             methyl                                                                   benzyl                                                                O O H    H     2,4,6-trimethylphenyl                                                                             212-213                                      O O 4-Cl H     methyl             122-124                                      O O H    H     3,4-difluorophenyl                                              O O 6-NO.sub.2                                                                          C.sub.2 H.sub.5                                                                      2,5-dichlorobenzyl                                              O O H    H                                                                                     ##STR10##         171-173                                      O O 4-CH.sub.3                                                                          H     ethyl              80-81                                        O O H    H     cyclododecyl       105-107                                      O O H    H     3-ispropylphenyl   98-100                                       S O H    C.sub.2 H.sub.5 OCH.sub.2                                                            n-butyl                                                         O O H    H     2-trifluoromethyl-                                                             phenyl                                                          O O H    H     cyclooctyl         103-105                                      O O H    H     4-methylphenyl     138-139                                      O O H    H     2,4-dibromophenyl                                               O O H    H     3-methyl-5-ethyl-  115-117                                                     phenyl                                                          O O H    H     methoxycarbonyl-   123-125                                                     methyl                                                          O O H    H     tert.-butyl        97- 99                                       O O H    H     4-ethoxyphenyl                                                  O O H    H     3-ethylphenyl      85-86                                        O O H    CH.sub.3                                                                             cycloheptyl                                                     O O H    H     2,6-dimethylphenyl 165-167                                      O O 5-CF.sub.3                                                                          H     isopropyl          121-123                                      O O 6-F  H     4-difluoromethoxy-                                                             phenyl                                                          O O H    H     3-methoxycarbonyl- 172-174                                                     aminophenyl                                                     O O H    H     2-methoxyphenyl                                                 O O H    H     tricyclo[4,3,1.sup.2,5 O.sup.1,6 ]                                                                103-105                                      O O H    H     2-methylphenyl     126-128                                      O O H    H     4-iodophenyl                                                    O O H    CH.sub.3                                                                             methyl             54-56                                        O O 4,6-Cl.sub.2                                                                        H     2-cyclohexylphenyl                                              O O H    H     3-methyl-4-chloro- 137-138                                                     phenyl                                                          O O H    H     3,5-dimethylcyclo- 128-129                                                     hexyl                                                           O O H    H     1-naphthyl         141-142                                      O O H    H     isopropyl          86-89                                        O O 6-Br H     ethyl                                                           O O H    H     4-nitrophenyl                                                   O O 6-F  H     methyl             116-118                                      O O 2-CH.sub.3                                                                          benzyl                                                                               ethyl                                                           O O 5-CF.sub.3                                                                          H     phenyl             133-135                                      O O 4-Br CH.sub.3                                                                             methyl                                                          O O H    H     2,6-dimethylcyclo- 121-123                                                     hexyl                                                           O O H    CH.sub.3 OCH.sub.3 -                                                                 3-fluorophenyl                                                  O O 6-OCH.sub.3                                                                         H     methyl             131-132                                      O O 2-CH.sub.3                                                                          CH.sub.3                                                                             benzyl                                                          O O 5-CF.sub.3                                                                          CH.sub.3                                                                             phenyl                                                          O O H    H     cycloheptyl        102-104                                      O O H    H     benzyl             113-115                                      O O 4-CH.sub.3                                                                          H     methyl                                                              6-NO.sub.2                                                                 O O 6-OCH.sub.3                                                                         H     phenyl             209-211                                      O O H    H     4-bromophenyl      136-137                                      S O H    H     phenyl                                                          O O H    H     3-methyl-5-iso-                                                                propylphenyl                                                    O S H    benzyl                                                                               n-butyl                                                         O O H    H     norbornyl          118-120                                      O O H    H     2-naphthyl                                                      S S 5-NO.sub.2                                                                          C.sub.2 H.sub.5                                                                      3-methylphenyl                                                  O O H    H     cyclopentyl        110-112                                      O O 6-Cl H     methyl             136-138                                      O S H    isopropyl                                                                            4-methylthiophenyl                                              O O H    H     3-methylcyclohexyl 120-122                                      S S H    H     methyl                                                          S O H    CH.sub.3                                                                             phenyl                                                          O S H    H     phenyl             156-158                                      S O H    H     ethyl                                                           S S H    H     phenyl                                                          O O H    C.sub.2 H.sub.5                                                                      phenyl             56-58                                        O O H    C.sub.2 H.sub.5                                                                      3-methylphenyl     75-77                                        O O H    H     hexahydrobenzyl    127-128                                      O O H    H     3,3,5-trimethyl-   79-82                                                       cyclohexyl                                                      O O H    H     3-(N,N-dimethylamino)-                                                         phenyl             126-127                                      O O H    H     3,4-(tetramethylene)-                                                          phenyl             164-166                                      O O H    H     cyclohexyl         117-118                                      O O H    H     2-methylcyclohexyl 100-102                                      O O H    H     1,3-dimethoxyiso-  95-96                                                       propyl                                                          O O H    H     tert.-amyl         62-63                                        O O H    H     2,3,6-trimethyl-   180-182                                                     phenyl                                                          O O H    H     2,3,5,6-tetramethyl-                                                                              237-238                                                     phenyl                                                          O O H    H     4-tert.-butylphenyl                                                                               113-115                                      O O H    H     2,3,5-trimethylphenyl                                                                             145-147                                      O O H    H     2-ispropyl-5-methyl-                                                                              103-105                                                     phenyl                                                          O O H    H     2-tert.-butyl-4-methyl-                                                        phenyl             154-156                                      O O H    H     2,6-dimethoxyphenyl                                                                               155-157                                      O O H    H     3-methylphenyl     106-108                                      O O H    C.sub.2 H.sub.5                                                                      3-methylphenyl     75-77                                        O O H    H     2-methyl-6-isopropyl-                                                          phenyl             122-124                                      O O H    H     3,5-diethylphenyl  128-130                                      O O H    H     1-adamantyl        113-115                                      O O H    H     1-methylcyclopentyl                                                                               57- 59                                       O O H    CH.sub.3                                                                             4-chlorophenyl      99-103                                      O O H    H     3,4,5-trimethoxy-  173-175                                                     phenyl                                                          O O H    H     2-methoxy-4-tert.-                                                             butyl-phenyl       151-153                                      O O H    H     2,4-ditert.-butyl-                                                             phenyl             186-187                                      O O H    CH.sub.3                                                                             2,4,6-trimethylphenyl                                                                             75-77                                        O O H    H     2,6-dichlorophenyl 156-158                                      O O H    H     2,3-dichlorophenyl 166-168                                      O O H    H     2,4,6-trichlorophenyl                                                                             171-173                                      O O H    CH.sub.3                                                                             4-chlorophenyl     94-96                                        O O H    H     2-acetylphenyl     109- 112                                     O O H    H     2-sec.-butylphenyl 72-74                                        O O H    H     2-ethylphenyl      115-117                                      O O H    H     2,5-dimethylphenyl 127-128                                      O O H    H     2-methyl-5-ispropyl-                                                           phenyl             146-147                                      O O H    H     2-isopropylphenyl  85-87                                        O O H    H     4-tert.-butylphenyl                                                                               84-86                                        O O H    H     4-methylcyclohexyl 122-126                                      __________________________________________________________________________

II. Aminourethanes EXAMPLE D

3 parts of a hydrogenation catalyst (palladium on animal charcoal, 10%) was added to a solution of 135 parts by weight of N-(3-nitrophenyl)-carbamic acid-4-chlorophenyl ester in 900 parts by weight of tetrahydrofuran (absolute); the mixture was then hydrogenated to constant weight at room temperature and a hydrogen pressure of 0.02 bar. The solution was freed from catalyst, dried with MgSO₄ and freed from solvent to such an extent that the crystalline reaction product was readily able to be filtered; 186°-187° C. ##STR11##

EXAMPLE E

While stirring intensively, 25.2 parts by weight of phenyl chloroforomate was dripped very slowly into a solution of 108 parts by weight of m-phenylenediamine in 1,000 parts by weight of water. After completion of the reaction, the mixture was suction filtered, the solid was washed several times with dilute hydrochloric acid, and the combined acidic solutions were neutralized with ammonia and suction filtered. The dried product thus obtained melts with decomposition at 178° to 180° C. ##STR12##

EXAMPLE F

While stirring intensively, 52.1 parts by weight of phenyl chloroformate is slowly dripped into 51 parts by weight of 2,4-diaminonitrobenzene and 43 parts by weight of sodium bicarbonate in 600 parts by weight of tetrahydrofuran. After the mixture has been stirred for 14 hours it is filtered and washed with tetrahydrofuran. The solution is freed from solvent to such an extent that the crude crystalline product can readily be filtered; after washing with diethyl ether and drying, the compound melts at 223° to 225° C. According to the nmr spectrum and elemental analysis, it has the following structure: ##STR13##

EXAMPLE G

While stirring intensively, 40 parts by weight of 3-(S-methylthiocarbamoyl)-nitrobenzene is added to a mixture, heated at 80° C., of 33 parts by weight of powdered iron, 75 parts by weight of alcohol, 60 parts by weight of water and 3 parts by weight of concentrated hydrochloric acid in such portions that the temperature is kept at 80° C. without additional heating. The mixture is refluxed for 1 hour and suction filtered while hot, the residue and the filtrate are digested with about 1,000 parts by weight of methylene chloride, followed by drying over sodium sulfate, concentration, and recrystallization from toluene; m.p.: 101°-103° C. ##STR14##

The following aminourethanes (F) may be prepared by analogous processes:

    __________________________________________________________________________      ##STR15##                                                                     A B X    R.sup.1                                                                               R.sup.3             m.p. °C.                            __________________________________________________________________________     O O H    H      4-fluorophenyl      166-167                                    O O H    H      2,4-dichlorophenyl  126-128                                    O O H    H      methyl              87-89                                      O O 6-CH.sub.3                                                                          H      methyl                                                         O O H    benzyl 4-chlorophenyl                                                 O O 4-NO.sub.2                                                                          H      methyl              187-189                                    O O H    H      3-methoxyphenyl                                                O O H    CH.sub.3                                                                              phenyl              70-72                                      O O H    H      2-fluorophenyl      172-173                                    O O 6-F  H      phenyl                                                         O O H    H      3-bromophenyl                                                  O O H    CH.sub.3 OCH.sub.2                                                                    3-methylphenyl                                                 S O H    H      methyl                                                         S S H    CH.sub.3                                                                              phenyl                                                         O S H    H      ethyl                                                          O S H    H      3-methylphenyl                                                 S O H    H      4-chlorophenyl                                                 S O H    H      phenyl                                                         O O H    H      3,4-dimethylphenyl  155-157                                    O O 5-CF.sub.3                                                                          H      methyl                                                         O O H    H      4-methoxyphenyl     146-149                                    O O 6-CH.sub.3                                                                          H      ethyl                                                          O O H    H      3-fluorophenyl      decomposes                                 O O H    H      ethyl               viscous oil                                O O 2-CH.sub.3                                                                          H      phenyl              131-133                                    O O H    H      2-chloro-4-fluoro-                                                             phenyl              decomposes                                 O O H    H      2-chlorophenyl      decomposes                                 O O 4,6-F.sub.2                                                                         H      methyl                                                         O S H    C.sub.2 H.sub.5                                                                       4-cyanophenyl                                                  O O 4-CH.sub.3                                                                          H      methyl                                                         O O H    H      3-trifluoromethyl-  126-128                                                    phenyl                                                         S O 2,5-Cl.sub.2                                                                        CH.sub.3                                                                              2-methoxyethyl                                                 O O H    H      4-trifluoromethyl-                                                             phenyl                                                         O O H    CH.sub.3                                                                              cyclododecyl                                                   O O H    H      4-ethylphenyl       160-161                                    O O 4-Cl H      phenyl              215-217                                    O O H    H      3-chloro-4-fluoro-                                                             phenyl                                                         S S 6-CH.sub.3                                                                          4-methyl                                                                              methyl                                                                  benzyl                                                                O O H    H      2,4,6-trimethylphenyl                                                                              150-152                                    O O 4-Cl H      methyl                                                         O O H    H      3,4-difluorophenyl                                             O S 6-NO.sub.2                                                                          C.sub.2 H.sub.5                                                                       2,5-dichlorobenzyl                                             O O H    H                                                                                      ##STR16##          184-186                                    O O 4-CH.sub.3                                                                          H      ethyl                                                          O O H    H      cyclododecyl        108-110                                    O O H    H      3-isopropylphenyl   68-70                                      O O H    H      3-ethyl-5-methyl-                                                              phenyl              102-104                                    S S H    H      phenyl                                                         O O H    H      3,3,5-trimethylcyclo-                                                          hexyl               100-102                                    O O H    H      2-methylcyclohexyl                                             O O H    C.sub.2 H.sub.5                                                                       3-methylphenyl      104-105                                    O O H    C.sub.2 H.sub.5                                                                       phenyl              104-106                                    S O H    C.sub.2 H.sub.5 OCH.sub.2                                                             n-butyl                                                        O O H    H      2-trifluoromethyl-                                                             phenyl                                                         O O H    H      cyclooctyl          77-79                                      O O H    H      4-methylphenyl      158-162                                    O O H    H      2,4-dibromophenyl                                              O O H    H      tert.-butyl         109-110                                    O S H    H      4-ethoxyphenyl                                                 O O H    H      3-ethylphenyl       112-114                                    O O H    CH.sub.3                                                                              cycloheptyl                                                    O O H    H      2,6-dimethylphenyl  160-161                                    O O 5-CF.sub.3                                                                          H      isopropyl           102-104                                    S O 6-F  H      4-difluoromethoxy-                                                             phenyl                                                         O O H    H      3-(O-methylcarbamoyl)-                                                                             149-151                                                    phenyl                                                         O O H    H      2-methoxyphenyl                                                O O H    H      tricyclo[4,3,1.sup.2,5 0.sup.1,6 ]-                                                                130-131                                                    decyl                                                          O O H    H      2-methylphenyl      170-172                                    O O H    H      4-iodophenyl                                                   O O H    CH.sub.3                                                                              methyl                                                         O S 4,6-Cl.sub.2                                                                        H      2-cyclohexylphenyl                                             O O H    H      3-methyl-4-chloro-  181                                                        phenyl                                                         O O H    H      3,5-dimethylcyclo-  80-82                                                      hexyl                                                          O O H    H      1-naphthyl          146-148                                    O O H    H      isopropyl           66-68                                      O S 6-Br H      ethyl                                                          S O H    H      4-nitrophenyl                                                  O O 6-F  H      methyl                                                         O O 2-CH.sub.3                                                                          benzyl ethyl                                                          O O 5-CF.sub.3                                                                          H      phenyl              214-216                                    S S 4-Br CH.sub.3                                                                              methyl                                                         O O H    H      2,6-dimethylcyclo-                                                             hexyl                                                          O O H    H      hexahydrobenzyl     106-108                                    O O H    H      2-ethylhexyl        viscous oil                                O S H    H      phenyl                                                         S O H    CH.sub.3 OCH.sub.2                                                                    3-fluorophenyl                                                 O O 6-OCH.sub.3                                                                         H      methyl                                                         O S 2-CH.sub.3                                                                          CH.sub.3                                                                              benzyl                                                         O S 5-CF.sub.3                                                                          CH.sub.3                                                                              phenyl                                                         O O H    H      cycloheptyl         86-88                                      O O H    H      benzyl                                                         S O 4-CH.sub.3                                                                          H      methyl                                                             6-NO.sub.2                                                                 O O 6-OCH.sub.3                                                                         H      phenyl              84-86                                      O O H    H      3-methyl-5-isopropyl-                                                          phenyl                                                         O S H    benzyl n-butyl                                                        O O H    H      norbornyl           133-135                                    O O H    H      2-naphthyl                                                     O S 5-NO.sub.2                                                                          C.sub.2 H.sub.5                                                                       3-methylphenyl                                                 O O H    H      cyclopentyl                                                    O O 6-Cl H      methyl                                                         S S H    isopropyl                                                                             4-methylthiophenyl                                             O O H    H      3-methylcyclohexyl  95-97                                      O O H    CH.sub.3                                                                              3-methylphenyl      112-115                                    O O H    H      3-(N,N-dimethylamino)-                                                         phenyl              132-133                                    O O H    H      3,4(tetramethylene)                                                            phenyl              181-183                                    O O H    H      methoxycarbonylmethyl                                          S S H    H      methyl                                                         O O H    H      2-isopropyl-5-methyl-                                                          phenyl              122-123                                    O O H    H      3-methylphenyl      142-144                                    O O H    H      2-tert.-butyl-4-methyl-                                                        phenyl              89-91                                      O O H    H      tert.-amyl          65-67                                      O O H    H      4-tert.-butylphenyl 175-177                                    O O H    H      2,3,5-trimethylphenyl                                                                              152-154                                    O O H    H      2,3,6-trimethyl-    155-156                                                    phenyl                                                         O O H    H      3,5-diethylphenyl   121-123                                    O O H    H      cyclohexyl          122-124                                    O O H    H      2-methylcyclohexyl                                             O O H    H      1,3-dimethoxyisopropyl                                         O O H    H      2-methyl-6-isopropyl-                                                          phenyl              133-135                                    O O H    CH.sub.3                                                                              2,4,6-trimethylphenyl                                          O O H    H      4-methylcyclohexyl  73-75                                      O O H    H      1-adamantyl         158-161                                    O O H    H      1-methylcyclopentyl                                            O O H    CH.sub.3                                                                              4-chlorophenyl      88-90                                      O O H    H      3,4,5-trimethoxy-   146-148                                                    phenyl                                                         O O H    H      2-methoxy-4-methyl  110-112                                                    phenyl                                                         O O H    H      2-methyl-4-tert.-                                                              butylphenyl         185-186                                    O O H    CH.sub.3                                                                              2,4,6-trimethylphenyl                                          O O H    H      2,4-di-tert.-butyl-                                                            phenyl              195-197                                    O O H    H      2-sec.-butylphenyl  75-77                                      O O H    H      2-ethylphenyl       74-75                                      O O H    CH.sub.3                                                                              4-fluorophenyl      123-125                                    O O H    H      2,5-dimethylphenyl  142-144                                    O O H    H      2-methyl-5-isopropyl-                                                          phenyl              139-141                                    O O H    H      2,3-dimethylphenyl  184-186                                    O O H    H      2-isopropylphenyl   80-82                                      __________________________________________________________________________

III. Diurethanes EXAMPLE 1

11 parts by weight of sodium bicarbonate was added to a solution of 22.8 parts by weight of N-(3-aminophenyl)-carbamic acid phenyl ester in 200 parts by weight of tetrahydrofuran (absolute); at 20° to 25° C. and with cooling, 13.3 parts by weight of thiomethyl chloroformate was then metered in. To complete the reaction, the mixture was stirred for 1 hour at room temperature. The reaction mixture was then filtered and the filtrate concentrated in vacuo. The only residue was crystallized by adding toluene; m.p.: 155°-157° C. (No. 1). The compound has the following structural formula: ##STR17##

EXAMPLE 2

A mixture of 20 parts by weight of N-(3-isothiocyanatophenyl)-O-methylcarbamate (obtainable from N-(3-aminophenyl)-O-methylcarbamate and thiophosgene, m.p. 99°-100° C.), 20 parts by weight of methanol, 3 parts by weight of triethylamine and 150 parts by weight of toluene is boiled for 6 hours. After concentration, the residue is recrystallized from toluene; m.p.: 147°-149° C. (No. 2). The compound has the following structural formula: ##STR18##

EXAMPLE 3

At room temperature, 10 parts by weight of carbon disulfide is dripped into a solution of 16.6 parts by weight of N-(3-aminophenyl)-O-methyl urethane and 10.1 parts by weight of triethylamine in 300 parts by weight of diethyl ether. After the mixture has been stirred for 20 hours it is suction filtered, the residue is suspended in 120 parts by weight of water, and 9.1 parts by volume of diethyl sulfate is added while stirring. After this mixture has been stirred for 20 hours, it is suction filtered, washed with water and air-dried; m.p.: 122°-124° C. (No. 3). The compound has the following structural formula: ##STR19##

The following compounds may be prepared analogously:

    __________________________________________________________________________      ##STR20##                                                                     No. A B D E X    R.sup.1                                                                              R.sup.2   R.sup.3     R.sup.4      m.p.°C.       __________________________________________________________________________     4   O S O O H    H     H         ethyl       phenyl       162-164              5   O S O O 2-CH.sub.3                                                                          H     H         methyl      phenyl       180-182              6   O O S O H    H     H         methyl      phenyl       155-157              7   O O S O H    H     H         phenyl      n-propyl     120-122              8   O S O O H    H     H         methyl      4-chlorophenyl                                                                              197-198              9   O S O O H    H     CH.sub.3  methyl      3-methylphenyl                                                                              118-120              10  O S O O H    H     H         3,3-dichloro-2-                                                                            phenyl       220-222                                               methylallyl                                   11  S S O O H    H     H         methyl      3-ethylphenyl                                                                               135-138              12  O S O O 5-CF.sub.3                                                                          H     H         methyl      phenyl       68-71                13  O O S O H    H     H         methyl      methyl       144-146              14  O O S O H    CH.sub.3                                                                             H         3-methylphenyl                                                                             ethyl        120-121              15  O O S S H    H     H         methyl      methyl       148-150              16  O S O O H    H     H         n-butyl     phenyl       127-129              17  S S O O H    H     CH.sub.3  methyl      3-methylphenyl                                                                              viscous                                                                        oil                  18  O S O O 4-OCH.sub.3                                                                         H     H         methyl      phenyl       123-125              19  O O O S H    H     H         methyl      4-chlorophenyl                                                                              156-158              20  O O S O 6-Cl H     H         phenyl      methyl       183-185              21  O S S O H    H     H         methyl      methyl       186-188              22  O S O O H    H     H         2,3-dichloroallyl                                                                          phenyl       137-139              23  O S O O H    H     H         methyl      3-methoxycarbonyl-                                                                          179-181                                                           aminophenyl                       24  O S O O H    H     H         phenyl      phenyl       158-159              25  O S O O H    H     benzyl    methyl      4-chlorophenyl                    26  O S O O H    H     CH.sub.3  ethyl       phenyl       131-133              27  O O S O 5-CF.sub.3                                                                          H     H         isopropyl   phenyl       135-137              28  O O S O H    CH.sub.3 OCH.sub.2                                                                   H         3-methylphenyl                                                                             methyl                            29  O S O O H    H     H         methyl      2,4-dichlorophenyl                                                                          167-168              30  O S O O H    H     H         2-phenylethyl                                                                              phenyl       129-131              31  O O O S H    H     H         ethyl       3-bromophenyl                     32  O S O O H    H     H         methyl      3-bromophenyl                                                                               163-165              33  O O S O 6-OCH.sub.3                                                                         H     H         methyl      ethyl        115-117              34  O S O O H    H     H         methyl      3-methoxyphenyl                   35  O S O O H    H     H         ethyl       3-ethylphenyl                                                                               130-132              36  S S O O H    H     CH.sub.3  methyl      phenyl       96-97                37  O O S O H    H     H         4-methylphenyl                                                                             ethyl        167-169              38  O S O O H    H     H         methyl      4-cyanophenyl                     39  S S O O H    H     H         methyl      4-methylphenyl                                                                              142-144              40  S O O O 3,5-Cl.sub.2                                                                        H     CH.sub.3  1-naphthyl  2-methoxyethyl                    41  S O O O H    H     H         phenyl      methyl       164-167              42  O O S O H    C.sub.2 H.sub.5                                                                      H         3-methylphenyl                                                                             ethyl                             43  O O S S H    H     H         methyl      phenyl       148-150              44  S O O O H    H     H         4-trifluoromethyl                                                                          methyl                            45  O O S S H    H     H         4-fluorophenyl                                                                             methyl       135-138              46  S S S S H    H     H         methyl      phenyl                            47  S S O O H    H     H         methyl      phenyl       134-136              48  O O S O H    H     H         methoxycarbonyl-                                                                           phenyl                                                             methyl                                        49  O S O O H    H     H         ethyl       4-fluorophenyl                                                                              152-154              50  O S O O H    H     H         methyl      cyclododecyl 162-164              51  O O O S H    H     H         methyl      4-methylphenyl                                                                              148-150              52  O O S O H    H     H         3-chloro-4-fluoro-                                                                         methyl                                                             phenyl                                        53  O S O O H    H     H         methyl      4-tert.-butylcyclo-                                                                         117-119                                                           hexyl                             54  O O S O H    H     H         tert.butyl  ethyl        128-130              55  O S O O H    H     4-methyl- methyl      phenyl                                                   benzyl                                                  56  O S O O H    H     H         ethyl       4-tert.butylcyclo-                                                                          103-105                                                           hexyl                             57  O O S O 4-Cl H     H         4-methylthiophenyl                                                                         methyl                            58  O O S O H    H     H         norbornyl   methyl       139-141              59  O O S O H    H     H         cyclooctyl  methyl       138-140              60  O S O O H    CH.sub.3                                                                             H         methyl      phenyl                            61  O S O O H    H     CH.sub.3  methyl      phenyl       118-120              62  O O S O H    H     H         3,4-difluorophenyl                                                                         methyl                            63  O S S O H    H     H         phenyl      methyl       148-150              64  O O S O H    H     H         methyl      2,4-dichlorobenzyl                65  O O S O H    H     H         methyl      benzyl       117-119              66  S O O O H    H     H         methyl      cyclododecyl                      67  O S O O H    H     C.sub.2 H.sub.5                                                                          methyl      3-methylphenyl                                                                              128-130              68  O O S O H    H     H         phenyl      benzyl       148-149              69  O S O O H    H     H         methyl      cyclopentyl                       70  O S O O H    H     H         methyl      tert.butyl   142-144              71  S S S O 4-CH.sub.3                                                                          H     H         methyl      phenyl                            72  O S O S 6-CH.sub.3                                                                          H     H         phenyl      phenyl                            73  O S O O H    H     H         methyl      1-naphthyl   195-196              74  S O S S H    H     H         propargyl   methyl                            75  O S O O 2-CH.sub.3                                                                          H     H         ethyl       4-tert.butylphenyl                76  O S O O H    H     H         methyl      2-fluorophenyl                                                                              183-185              77  O S S S H    H     H         n-propyl    phenyl                            78  O O S O H    H     H         3-fluorophenyl                                                                             methyl       161-162              79  S O O S H    H     H         methyl      phenyl                            80  O S O O H    H     H         methyl      4-fluorophenyl                                                                              171-173              81  S S O S H    H     H         methyl      phenyl                            82  O O S O H    H     H         2-chlorophenyl                                                                             methyl       183-184              83  S S S O H    H     H         methyl      phenyl                            84  O S O O 4-CH.sub.3                                                                          H     H         methyl      4-methylphenyl                    85  O O S O H    H     H         2-methylphenyl                                                                             methyl       176-177              86  S O O S H    H     H         methyl      2-methylphenyl                    87  O S O O H    H     H         methyl      4-methylphenyl                                                                              188-190              88  O S O S H    H     H         phenyl      methyl                            89  O S S S H    H     H         4-chlorophenyl                                                                             methyl                            90  O S O O H    H     H         methyl      3-ethylphenyl                                                                               118-120              91  O S S S 6-CH.sub.3                                                                          H     H         4-chlorophenyl                                                                             ethyl                             92  O S O O H    H     H         methyl      4-ethylphenyl                                                                               186-188              93  O S O S H    H     H         methyl      4-chlorophenyl                    94  O O S O H    H     H         3-trifluoromethyl-                                                                         methyl       140-142                                               phenyl                                        95  S O O O 4-NH.sub.2                                                                          H     H         sec.butyl   propargyl                         96  O S O O H    H     H         methyl      4-methoxyphenyl                                                                             185-186              97  S O O S H    H     H         sec.amyl    methyl                            98  O S O O H    H     H         methyl      3,4-dimethylphenyl                                                                          180-182              99  S O S O H    H     H         3-methylphenyl                                                                             methyl                            100 O O S O H    H     H         2-chloro-4-fluoro-                                                                         methyl       183-184                                               phenyl                                        101 S S S O 4-OCH.sub.3                                                                         H     H         methyl      phenyl                            102 O S O O H    H     H         ethyl       3-isopropylphenyl                                                                           107-109              103 O O S O H    H     H         2,6-dimethylphenyl                                                                         methyl       110-112              104 O S S S H    H     H         cyclododecyl                                                                               ethyl                             105 O S O O H    H     H         methyl      2,4,6-trimethyl-                                                                            188-190                                                           phenyl                            106 O O S O H    CH.sub.3                                                                             H         4-methylphenyl                                                                             ethyl                             107 O S O O H    H     H         methyl      5-indanyl    193-194              108 S S O S 4-NO.sub.2                                                                          H     H         methyl      methyl                            109 O O S O H    H     H         3-(N,N-dimethyl-                                                                           ethyl                                                              amino)-phenyl                                 110 S O O O H    H     H         phenyl      methoxycarbonyl-                                                               methyl                            111 O S O O H    H     H         methyl      3,4-(tetramethyl-                                                                           163-165                                                           ene)-phenyl                       112 O O O S H    H     H         2-cyclohexyl-                                                                              methyl                                                             phenyl                                        113 O O S S H    H     H         3,4-(tetramethyl-                                                                          methyl                                                             ene)-phenyl                                   114 O S O S H    H     H         methyl      2-naphthyl                        115 O S O O H    H     H         methyl      3-methyl-5-ethyl-                                                                           120-122                                                           phenyl                            116 O O S O H    H     H         3,4-(tetramethyl-                                                                          ethyl                                                              ene)-phenyl                                   117 S O S S H    H     H         methyl      phenyl                            118 O S O O H    H     H         methyl      3-isopropylphenyl                                                                           104-106              119 S S O S 6-NO.sub.2                                                                          H     H         methyl      4-methylphenyl                    120 O O S O H    H     H         3-methyl-5-ethyl-                                                                          ethyl                                                              phenyl                                        121 O O O S H    H     H         2-naphthyl  methyl                            122 O S O O H    H     H         methyl      3-(N,N-dimethyl-                                                                            163-165                                                           amino)-phenyl                     123 O S O S 4-Br H     H         methyl      2-trifluoromethyl-                                                             phenyl                            124 O S O O H    H     H         methyl      methoxycarbonyl-                                                                            116-118                                                           methyl                            125 S S S O H    H     H         methyl      4-methylphenyl                    126 S S O O H    H     H         methyl      tert.butyl   101-103              127 O S O S 6-Br H     H         allyl       tert.butyl                        128 O S S O H    CH.sub.3                                                                             H         phenyl      ethyl                             129 O O S O H    H     H         3,3,5-trimethyl-                                                                           ethyl        oil                                                   cyclohexyl                                    130 S O O O H    H     H         phenyl      tert.butyl   143-147              131 O O S O H    Isopropyl                                                                            H         phenyl      methyl                            132 O S O O H    H     H         methyl      cyclohexyl   145-146              133 O S S O H    CH.sub.3                                                                             H         methyl      phenyl                            134 O S O O H    H     H         methyl      3,5-dimethylcyclo-                                                                          129-131                                                           hexyl                             135 O O S S H    H     H         tert.butyl  phenyl                            136 S S O S 4-F  H     H         methyl      benzyl                            137 O S O O H    H     H         ethyl       tricyclo-    oil                                                               (4,3,1.sup.2,5 0.sup.1,6)-dec                                                  yl                                138 O O S O H    H     H         3-methylcyclohexyl                                                                         ethyl        oil                  139 S S S O H    H     H         methyl      n-butyl                           140 O S O O H    H     benzyl    methyl      4-fluorophenyl                    141 O S S S H    H     H         methyl      phenyl       155-157              142 S O S S 4,6-F.sub.2                                                                         H     H         4-iodophenyl                                                                               methyl                            143 O O S O H    H     H         tert.butyl  phenyl                            144 O S O O H    H     H         methyl      3-methyl-4-chloro-                                                                          162-164                                                           phenyl                            145 O S O O H    H     H         ethyl       2,6-dimethylcyclo-                                                             hexyl                             146 O S S O H    CH.sub.3                                                                             H         phenyl      methyl                            147 O S O O H    H     H         methyl      4-difluoromethoxy-                                                             phenyl                            148 O O S O H    H     H         2-ethylhexyl                                                                               ethyl        oil                  149 O S O O H    H     H         methyl      2,6-dimethylcyclo-                                                                          64-66                                                             hexyl                             150 O S O O H    H     H         methyl      3,3,5-trimethylcyclo-                                                                       57-60                                                             hexyl                             151 O S O O H    H     H         methyl      3-methylcyclohexyl                                                                           98-100              152 O S O O H    H     H         methyl      cycloheptyl                       153 O S O O H    H     H         ethyl       cycloheptyl                       154 S O S O H    H     H         methyl      4-((CH.sub.3).sub.2 NSO.sub.2                                                  )phenyl                           155 O S O O H    CH.sub.3                                                                             H         methyl      methyl                            156 S O S S 6-F  H     H         4-methylthiophenyl                                                                         n-propyl                          157 S S S S H    H     H         3-isothiocyanato                                                                           2-chloroethyl                     158 O O S O H    CH.sub.3                                                                             H         methyl      phenyl       163-165              159 S O S O 4-NO.sub.2                                                                          H     H         4-benzoylphenyl                                                                            allyl                             160 O S S S H    H     H         isopropyl   phenyl                            161 S S S O H    H     H         methyl      methyl       146-148              162 S S O S H    H     H         methyl      3-phenoxyphenyl                   163 S O S O H    H     H         phenyl      methyl       186-188              164 S O O S 6-F  H     H         methyl      4-chlorobutyn-2-yl-1              165 S O S O H    H     H         methyl      3-(1'-ethoxycarbonyl-                                                          ethoxy)-phenyl                    166 O S O O H    H     C.sub.2 H.sub.5                                                                          ethyl       phenyl       140-142              167 S O O S H    H     H         methyl      cyclohexyl                        168 S S S S H    H     H         n-decyl     methyl                            169 O O S O H    ClCH.sub.2                                                                           H         phenyl      methyl                            170 S O S O H    H     H         4-methylphenyl                                                                             methyl       191-193              171 O S O O H    H     H         3-acetylphenyl                                                                             2-methoxyethyl                    172 O S O O H    H     H         methyl      propargyl    104-105              173 S O O O H    H     H         propargyl   3(CH.sub.3 SO.sub.3)-phenyl       174 O S O O H    H     H         methyl      2-ethylhexyl 89-91                175 S O S S H    H     H         sec.butyl   n-butyl                           176 O O S O H    C.sub.2 H.sub.5                                                                      H         phenyl      methyl       140-142              177 O O S O 4-F  H     H         4(CH.sub.3 SO.sub.2)-phenyl                                                                methyl                            178 O S O O H    H     H         phenyl      ethyl                             179 S O O O H    H     H         phenyl      ethyl                             180 S O O O H    H     H         phenyl      isopropyl                         181 O S O O H    H     H         methyl      isopropyl    135-136              182 S S S S H    H     H         3-methylphenyl                                                                             allyl                             183 O S O O H    H     CH.sub.3 OCH.sub.2                                                                       methyl      phenyl                            184 O S O O H    CH.sub.3                                                                             H         phenyl      methyl                            185 O O S O H    H     H         3-aminophenyl                                                                              methyl                            186 S O O O H    H     H         4-methylphenyl                                                                             ethyl                             187 O S O O H    H     CH.sub.3  methyl      4-chlorophenyl                                                                              149-152              188 O O S O H    CH.sub.3                                                                             H         4-methylphenyl                                                                             methyl                            189 O O S O H    H     CH.sub.3  methyl      4-chlorophenyl                    190 O S S O H    H     CH.sub.3  phenyl      ethyl                             191 O O S O H    H     CH.sub.3  phenyl      ethyl                             192 O S O O H    H     CH.sub.3  phenyl      ethyl                             193 S O S S 4-OC.sub.2 H.sub.5                                                                  H     H         ethyl       4-phenoxyphenyl                   194 S S S S H    H     H         methyl      4-fluorophenyl                    195 O O S O H    H     CH.sub.3  methyl      4-methylphenyl                    196 O O O S H    H     H         phenyl      methyl       155                  197 S O O O 6-Cl H     H         phenyl      methyl       135-137              198 O S O O H    H     H         methyl      ethyl                             199 O S O O H    H     H         methyl      2,3,6-trimethyl-                                                                            196-198                                                           phenyl                            200 O S O O H    H     CH.sub.3  methyl      methyl                            201 O O S O H    H     H         2,3,5-trimethyl-                                                                           methyl       189-191                                               phenyl                                        202 O S O O H    H     CH.sub.3  methyl      2,3,5-trimethyl-                                                               phenyl                            203 O S O O H    H     CH.sub.3  methyl      2,3,6-trimethyl-                                                               phenyl                            204 O S O O H    H     CH.sub.3  methyl      2,4,6-trimethyl-                                                                            196-198                                                           phenyl                            205 S S O O H    H     CH.sub.3  methyl      2,4,6-trimethyl-                                                                            157-159                                                           phenyl                            206 O O S O H    H     H         tert.amyl   methyl       91-93                207 O S O O H    H     H         methyl      1,3-dimethoxyiso-                                                              propyl                            208 O O S O H    H     H         1-chloroisopropyl                                                                          methyl                            209 O S O O H    H     H         methyl      hexahydrobenzyl                                                                             110-112              210 O O S O H    H     H         benzyl      methyl       146-147              211 O S O O H    H     H         methyl      1,1-dimethyl-2-                                                                             117-120                                                           chloroethyl                       212 O O S O H    H     H         4-methylcyclohexyl                                                                         methyl       152-155              213 O S O O H    H     H         methyl      2-methylcyclohexyl                214 O O S O H    H     H         1-methylcyclo-                                                                             methyl       89-92                                                 pentyl                                        215 O O S O H    H     H         1-adamantyl methyl       134-137              216 O S O O H    H     H         methyl      butyn-1-yl-3-                                                                               128-129              217 O S S O H    H     H         benzyl      methyl       125-127              218 O S S O H    H     H         methyl      3-methylphenyl                                                                              145-147              219 O S O O H    H     H         ethyl       3-methylphenyl                                                                              126-128              220 O O S O H    H     H         2-ethylphenyl                                                                              methyl       160-162              221 O S O O H    H     H         methyl      2-isopropylphenyl                                                                           125-127              222 O S O O H    H     H         methyl      4-isopropylphenyl                                                                           145-147              223 O S O O H    H     H         methyl      4-tert.butylphenyl                                                                          100-102              224 O S O O H    H     H         ethyl       4-tert.butylphenyl                                                                          140-142              225 O S O O H    H     H         methyl      2-sec.butylphenyl                                                                           127-129              226 O S O O H    H     H         methyl      4-bromophenyl                                                                               186-188              227 O S O O H    H     H         methyl      4-(S-methylthio-                                                                            203-206                                                           carbamoyl)-phenyl                 228 O O S O H    H     H         3,4,5-trimethoxy-                                                                          methyl       155-157                                               phenyl                                        229 O O S O H    H     H         2-isopropyl-5-                                                                             methyl       162-164                                               methylphenyl                                  230 O S O O H    H     H         methyl      2-tert.butyl-4-                                                                             171-173                                                           methylphenyl                      231 O S O O H    H     H         methyl      2-methyl-6-iso-                                                                             152-153                                                           propylphenyl                      232 O O S 0 H    H     H         3,5-diethylphenyl                                                                          methyl       132-134              233 O O S O H    H     H         2-methyl-4-tert.-                                                                          methyl       150-152                                               butylphenyl                                   234 O S O O H    H     H         methyl      2,4-di-tert.butyl-                                                                          157-158                                                           phenyl                            235 O S O O H    H     H         methyl      2-methyl-5-iso-                                                                             127-129                                                           propylphenyl                      236 O O S O H    H     H         2,3-dimethylphenyl                                                                         methyl       185-187              237 O O S O H    H     H         2,5-dimethylphenyl                                                                         methyl       159-161              238 O S O O H    H     H         methyl      2,3,5,6-tetra-                                                                              240-241                                                           methylphenyl                      239 O S O O H    H     H         methyl      2-chloro-4,5-                                                                               192-194                                                           dimethylphenyl                    240 O O S O H    H     H         2-methoxyphenyl                                                                            methyl       162-164              241 O S O O H    H     H         methyl      2-methoxy-4- 140-142                                                           methylphenyl                      242 O S O O H    H     H         methyl      2-nitro-4-methyl-                                                                           118-120                                                           phenyl                            243 O O S O H    H     H         2,4,6-trichloro-                                                                           methyl       171-173                                               phenyl                                        244 O S O O H    H     H         methyl      2,4,5-trichloro-                                                                            173-175                                                           phenyl                            245 O S O O H    H     H         methyl      2,3-dichlorophenyl                                                                          178-179              246 S S O O H    H     CH.sub.3  methyl      4-chlorophenyl                                                                              88-90                247 S S O O H    H     CH.sub.3  methyl      4-fluorophenyl                                                                              105-107              248 O S O O H    H     CH.sub.3  methyl      4-fluorophenyl                                                                              153-155              249 O S S O H    CH.sub.3                                                                             H         methyl      methyl       169-171              250 S S O O H    H     C.sub.2 H.sub.5                                                                          methyl      phenyl       104-106              251 O S O O H    H     H         methyl      4-sec.butylphenyl                 __________________________________________________________________________      ##STR21##                                                                     No. A B D E X    R.sup.1                                                                              R.sup.2   R.sup.3     R.sup.4      m.p.°C.       __________________________________________________________________________     252 O O S S H    H     H         3,3-dimethyl-5-                                                                            CH.sub.3     145-147                                               methyl-cyclohexyl                             253 O S O O H    H     CH.sub.2COOCH.sub.3                                                                      CH.sub.3    phenyl       115-117              254 O O S O H    H     H         CH.sub.3    tert,.butyl  133-135              255 O S O O H    H     CH.sub.2CH.sub.2Cl                                                                       CH.sub.3    phenyl                            256 O S O O H    H     H         tert.butyl  C.sub.2 H.sub.5                                                                             96-98                257 O S O O H    H     H         tert.butyl  phenyl       159-161              258 O S S O H    H     H         tert.butyl  methyl       132-134              259 O S O O H    H     CH.sub.3  tert.butyl  phenyl       148-150              260 O S O O H    H     H         tert.butyl  norbornyl    205-207              261 O S O O H    H     propyl    methyl      phenyl       138-140              __________________________________________________________________________

In the following experiments, prior art herbicidal active ingredients were used for comparison purposes.

Methyl-N-(3-(N'-(3'-methylphenyl)-carbamoyloxy)-phenyl)-carbamate and ethyl-N-(N'-phenylcrbamoyloxy)-phenyl-carbamate (German Printed Application DAS No. 1,567,151) are characterized by their--albeit different--action on broadleaved unwanted plants and are well tolerated by sugarbeets. However, as is known, the selectivity of the former compound is better in this crop than that of the latter. The range of application for 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide (German Printed Application No. 1,542,836) is completely different. This compound is used to combat various broadleaved weeds in soybeans, groundnuts, cereals, Indian corn and some vegetable species. However, there are gaps in the action. Methyl-N-(3-N'-methyl-N'-phenylcarbamoyloxy)-phenyl-carbamate has a herbicidal action good for its class, but hardly any crop plant selectivity; for this reason, the compound has only been recommended for instance in soybeans for post-directed use (Arndt, F. and G. Boroschewsky: New Selective Herbicides, VIII International Plant Protection Congress, Reports and Information, Section III, Chemnical Control, Part I, Moscow, 1975, pp. 42-49). In this method, the young shoots and leaves of the crop plants are not contacted by the spray liquor, which is used to treat the unwanted plants growing beneath them.

Examples demonstrating the herbicidal action of the novel sulfurous diurethanes

Numerous test results give proof of the good herbicidal properties of the novel compounds. Their herbicidal potency and their selectivity in crop plants are demonstrated in the following examples.

Greenhouse experiments

Plastic flowerpots having a volume of 300 cm³ were filled with a sandy loam and test plants, separated by species, were placed therein. Predominantly, seeds were sown or vegetatively reproducing species were transplanted. The active ingredients were suspended or emulsified in water as vehicle and sprayed (postemergence treatment) by means of finely distributing nozzles on to the leaves of the test plants and the surface of the soil. For the postemergence treatment, the plants were grown in the pots to a height of from 3 to 10 cm, depending on habit, before being treated. Depending on the temperature requirements of the plants, they were placed in either cooler or warmer sections of the greenhouse. The experiments were run for from 2 to 4 weeks. During the experimental period, the plants were tended and their reaction to the individual treatments was evaluated. The application rates of the compounds are given in kg/ha of active ingredient. The scale for assessment of the activity was 0 to 100, 0 denoting no damage, and 100 complete destruction of the plants.

Results

The figures in the following tables illustrate the action of the active ingredients on treatment after emergence of the crop and unwanted plants (Tables 2 to 12). It is worthy of note that the herbicidal effectiveness and spectrum of action of the new compounds tend toward those of the diurethanes used for comparison purposes. However, their selectivity in crop plants is not the same. This can be excellently exemplified by the results in soybeans and cereals. These crops tolerate the new compounds to the same extent as 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, which is known to be well tolerated in these crops (Tables 5,6). In addition, there are a number of crop plants whose tolerance precisely of the compounds according to the invention is conspicuous, whereas the comparative agents are unsuitable (Tables 2, 4, 5).

Possible application methods are soil incorporation or treatment of the soil surface, but the treatment of emerged plants is preferred. Special applications, such as post-directed or lay-by spraying, are also suitable. The jet is directed here in such a manner that the leaves of the sensitive crop plants are if possible not contacted; the agents thus reach the surface of the soil or the unwanted plants growing there.

In view of the variety of application methods, the agents according to the invention or compositions containing them may be used for removing unwanted plants from a much larger number of crop plants than those given in the tables. Application rates may be 0.1 to 15 kg/ha and more, depending on the objective to be achieved.

Crop plants in which the compounds according to the invention may be used are as follows:

    ______________________________________                                         Botanical term     Common name                                                 ______________________________________                                         Allium cepa        onions                                                      Ananas comosus     pineapples                                                  Asparagus officinalis                                                                             asparagus                                                   Avena sativa       oats                                                        Beta vulgaris spp. altissima                                                                      sugarbeets                                                  Beta vulgaris spp. rapa                                                                           fodder beets                                                Beta vulgaris spp. esculenta                                                                      table beets, red beets                                      Brassica napus var. napus                                                                         rape                                                        Brassica napus var. napobrassica                                               Brassica napus var. rapa                                                                          turnips                                                     Brassica rapa var. silvestris                                                  Camellia sinensis  tea plants                                                  Citrus limon       lemons                                                      Citrus maxima      grapefruits                                                 Citrus reticulata                                                              Citrus sinensis    orange trees                                                Coffea arabica (Coffea canephora,                                              Coffea liberica)   coffee plants                                               Cucumis melo       melons                                                      Cucumis sativus    cucumbers                                                   Cynodon dactylon   Bermudagrass in turf                                                           and lawns                                                   Elaeis guineensis  oil palms                                                   Fragaria vesca     strawberries                                                Gossypium hirsutum                                                             (Gossypium arboreum                                                            Gossypium herbaceum                                                            Gossypium vitifolium)                                                                             cotton                                                      Helianthus annuus  sunflowers                                                  Helianthus tuberosus                                                           Hevea brasiliensis rubber plants                                               Hordeum vulgare    barley                                                      Humulus lupulus    hops                                                        Ipomoea batatas    sweet potatoes                                              Lactuca sativa     lettuce                                                     Lens culinaris     lentils                                                     Linum usitatissimum                                                                               flax                                                        Lycopersicon lycopersicum                                                                         tomatoes                                                    Malus spp.         apple trees                                                 Manihot esculenta  cassava                                                     Medicago sativa    alfalfa (lucerne)                                           Mentha piperita    peppermint                                                  Musa spp.          banana plants                                               Nicotiana tabacum                                                              (N. rustica)       tobacco                                                     Olea europaea      olive trees                                                 Oryza sativa       rice                                                        Panicum miliaceum                                                              Phaseolus lunatus  limabeans                                                   Phaseolus mungo    mungbeans                                                   Phaseolus vulgaris snapbeans, green beans,                                                        dry beans                                                   Pinnisetum glaucum                                                             Petroselinum crispum                                                           spp. tuberosum     parsley                                                     Picea abies        Norway spruce                                               Albies alba        fir                                                         Pinus spp.         pine trees                                                  Pisum sativum      English peas                                                Prunus avium       cherry trees                                                Prunus domestica   plum trees                                                  Prunus persica     peach trees                                                 Pyrus communis     pear trees                                                  Ribes sylvestre    redcurrants                                                 Ribis uva-crispa                                                               Ricinus communis                                                               Saccharum officinarum                                                                             sugar cane                                                  Secale cereale     rye                                                         Sesamum indicum    Sesame                                                      Solnum tuberosum   Irish potatoes                                              Sorghum bicolor (s. vulgare)                                                                      grain sorghum                                               Sorghum dochna                                                                 Spinacia oleracea  spinach                                                     Theobroma cacao    cacao plants                                                Trifolium pratense red clover                                                  Vaccinium corymbosum                                                                              blueberries                                                 Vaccinium vitis-idaea                                                                             cranberries                                                 Vicia faba         tick beans                                                  Vigna sinensis (V. unguiculata)                                                                   cow beans                                                   Vitis vinifera     grapes                                                      ______________________________________                                    

To broaden the spectrum of activity of the new individual compounds, to achieve synergistic effects or to improve the residual action in the soil, the new compounds may be intermixed, or numerous other herbicical or growth-regulating compounds may be employed in compositions and combinations. Depending on the area of use and the objective, the following compounds or chemically similar derivatives are suitable for admixture with the compounds according to the invention:

    ______________________________________                                          ##STR22##                                                                     R                    R.sup.1                                                   ______________________________________                                          ##STR23##           NH.sub.2                                                   ##STR24##           NHCH.sub.3                                                 ##STR25##           NHCH.sub.3                                                 ##STR26##           NH.sub.2                                                  ______________________________________                                          ##STR27##                                                                     R         R.sup.1    R.sup.2                                                   ______________________________________                                                    ##STR28## H          and salts                                      H                                                                                         ##STR29## Cl         and salts                                      H                                                                                         ##STR30## F          and salts                                      H                                                                                         ##STR31## CH.sub.3   and salts                                      CH.sub.2 OCH.sub.3                                                                        ##STR32## H                                                          ##STR33##                                                                     ______________________________________                                          ##STR34##                                                                     R.sup.1     R.sup.2       R.sup.3                                              ______________________________________                                         CF.sub.3    n. C.sub.3 H.sub.7                                                                           n . C.sub.3 H.sub.7                                  CF.sub.3    n. C.sub.3 H.sub.7                                                                           CH.sub.2CH.sub.2 Cl                                  SO.sub.2 NH.sub.2                                                                          n. C.sub.3 H.sub.7                                                                           n . C.sub.3 H.sub.7                                  ______________________________________                                          ##STR35##                                                                     R.sup.1       R.sup.2  R.sup.3                                                 ______________________________________                                         CH.sub.3      H                                                                                        ##STR36##                                               ##STR37##    H        i-C.sub.3 H.sub.7                                        ##STR38##    H                                                                                        ##STR39##                                               ##STR40##    H                                                                                        ##STR41##                                               ##STR42##    H        i-C.sub.3 H.sub.7                                        ##STR43##    H        CH.sub.2CCCH.sub.2 Cl                                    ##STR44##    H                                                                                        ##STR45##                                               ##STR46##    H        CH.sub.3                                                 ##STR47##    H        CH.sub.3                                                 ##STR48##                                                                     ______________________________________                                          ##STR49##                                                                     R.sup.1        R.sup.2      R.sup.3                                            ______________________________________                                          ##STR50##     H            C.sub.2 H.sub.5                                     ##STR51##     CH.sub.3     CH.sub.3                                            ##STR52##     H            CH.sub.3                                            ##STR53##     H            C.sub.2 H.sub.5                                     ##STR54##     H            CH.sub.3                                            ##STR55##     H            C.sub.2 H.sub.5                                    ______________________________________                                          ##STR56##                                                                     R.sup.1    R.sup.2     R.sup.3                                                 ______________________________________                                         i-C.sub.3 H.sub.7                                                                         i-C.sub.3 H.sub.7                                                                          CH.sub.2CClCHCl                                         n. C.sub.3 H.sub.7                                                                        n. C.sub.3 H.sub.7                                                                         C.sub.2 H.sub.5                                         n. C.sub.3 H.sub.7                                                                        n. C.sub.3 H.sub. 7                                                                        n. C.sub.3 H.sub.7                                      sec. C.sub.4 H.sub.9                                                                      sec. C.sub.4 H.sub.9                                                                       C.sub.2 H.sub.5                                         C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                             ##STR57##                                               ##STR58## C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                          ##STR59## C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                          ##STR60##                                                                     ______________________________________                                          ##STR61##                                                                               R                                                                    ______________________________________                                                   C.sub.2 H.sub.5                                                                n. C.sub.3 H.sub.7                                                              ##STR62##                                                           ______________________________________                                          ##STR63##                                                                     R.sup.1         X       Y        R.sup.2                                       ______________________________________                                         CH.sub.3        Cl      Cl       Na                                            Cl              Cl      Cl       Na                                            C.sub.2 H.sub.5 Cl      Cl       Na                                             ##STR64##      Cl      H        CH.sub.3                                       ##STR65##      H       H        H and salts                                    ##STR66##      H       Cl       NH.sub.4                                       ##STR67##      H       CH.sub.3 C.sub.2 H.sub.5                                ##STR68##      H       CH.sub.3 CH.sub.3                                       ##STR69##      H       CH.sub.3 i-C.sub.3 H.sub.7                              ##STR70##      H       CH.sub.3                                                                                 ##STR71##                                     ##STR72##      H       CH.sub.3 CH.sub.3                                       ##STR73##                                                                      ##STR74##                                                                      ##STR75##                                                                     ______________________________________                                          ##STR76##                                                                     R.sup.1   X           R.sup.2                                                  ______________________________________                                         i-C.sub.3 H.sub.7                                                                        Cl          C.sub.2 H.sub.5                                          i-C.sub.3 H.sub.7                                                                        Cl                                                                                          ##STR77##                                               i-C.sub.3 H.sub.7                                                                        Cl          i-C.sub.3 H.sub.7                                        C.sub.2 H.sub.5                                                                          Cl          C.sub.2 H.sub.5                                          C.sub.2 H.sub.5                                                                          Cl          C(CH.sub.3).sub.2 CN                                     C.sub.2 H.sub.5                                                                          Cl                                                                                          ##STR78##                                               C.sub.2 H.sub.5                                                                          Cl                                                                                          ##STR79##                                                ##STR80##                                                                               Cl          C(CH.sub.3).sub.2CN                                      i-C.sub.3 H.sub.7                                                                        OCH.sub.3   i-C.sub.3 H.sub.7                                        i-C.sub.3 H.sub.7                                                                        SCH.sub.3   C.sub.2 H.sub.5                                          C.sub.2 H.sub.5                                                                          SCH.sub.3   C.sub.2 H.sub.5                                          C.sub.2 H.sub.5                                                                          SCH.sub.3   tert . C.sub.4 H.sub.9                                   ______________________________________                                          ##STR81##                                                                     X           Y             R                                                    ______________________________________                                         CF.sub.3    H             CH.sub.3                                             H           F             CH.sub.3                                             ______________________________________                                          ##STR82##                                                                     R.sup.1    R.sup.2         R.sup.3                                             ______________________________________                                          ##STR83##                                                                                 ##STR84##      CH.sub.2 Cl                                          ##STR85##                                                                                 ##STR86##      CH.sub.2 Cl                                          ##STR87## CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.2 Cl                                          ##STR88## CH.sub.2OCH.sub.3                                                                              CH.sub.2 Cl                                          ##STR89##                                                                                 ##STR90##      CH.sub.2 Cl                                          ##STR91## CH.sub.2OC.sub.4 H.sub.9 n                                                                     CH.sub.2 Cl                                          ##STR92##                                                                                 ##STR93##      CH.sub.2 Cl                                          ##STR94## H                                                                                               ##STR95##                                           ##STR96##       H                                                                                       ##STR97##                                             ##STR98##       H       C.sub.2 H.sub.5                                        ##STR99##       H       C(CH.sub.3).sub.2C.sub.3 H.sub.7                       ##STR100##      H       CH.sub.3                                               ##STR101##      H       CH.sub.3                                               ##STR102##      H                                                                                       ##STR103##                                            ##STR104##                                                                     ##STR105##                                                                    X        X.sub.1     R                                                         ______________________________________                                         Br       Br          H and salts                                               I        I           H and salts                                               Br       Br                                                                                          ##STR106##                                                ##STR107##                                                                    X = NO.sub.2                                                                   CN                                                                             ______________________________________                                          ##STR108##                                                                    R         R.sup.1    R.sup.2   R.sup.3                                         ______________________________________                                         Cl        Cl         Cl        H                                               F         Cl         Cl        H                                               Cl        Cl         H         H                                               Cl        CF.sub.3   H         COOH                                            Cl        Cl         H         COOCH.sub.3                                     NO.sub.2  CF.sub.3   H         H                                               H         CF.sub.3   Cl        H                                               H         CF.sub.3   Cl        OC.sub.2 H.sub.5                                Cl        Cl         H         OCH.sub.3                                       ______________________________________                                          ##STR109##                                                                    R.sup.1            R.sup.2                                                                              R.sup.3                                                                               R.sup.4                                        ______________________________________                                          ##STR110##        H     CH.sub.3                                                                              CH.sub.3                                        ##STR111##        H     CH.sub.3                                                                              CH.sub.3                                        ##STR112##        H     CH.sub.3                                                                              CH.sub.3                                        ##STR113##        H     CH.sub.3                                                                              CH.sub.3                                        ##STR114##        H     CH.sub.3                                                                              CH.sub.3                                        ##STR115##        H     CH.sub.3                                                                               ##STR116##                                     ##STR117##        H     CH.sub.3                                                                              CH.sub.3                                        ##STR118##        H     CH.sub.3                                                                              OCH.sub.3                                       ##STR119##        H     CH.sub.3                                                                              CH.sub.3                                        ##STR120##        H     CH.sub.3                                                                              OCH.sub.3                                       ##STR121##        H     CH.sub.3                                                                              CH.sub.3                                        ##STR122##        H     CH.sub.3                                                                              CH.sub.3                                        ##STR123##        H     CH.sub.3                                                                              OCH.sub.3                                       ##STR124##        H     CH.sub.3                                                                              CH.sub.3                                        ##STR125##        H     CH.sub.3                                                                              OCH.sub.3                                       ##STR126##        H     CH.sub.3                                                                              OCH.sub.3                                       ##STR127##        H     CH.sub.3                                                                              CH.sub.3                                        ##STR128##        CH.sub.3                                                                             H      CH.sub.3                                        ##STR129##                                                                     ##STR130##                                                                     ##STR131##                                                                    ______________________________________                                          ##STR132##                                                                    R           R.sup.1           R.sup.2                                          ______________________________________                                         tert. C.sub.4 H.sub.9                                                                      NH.sub.2          SCH.sub.3                                        tert. C.sub.4 H.sub.9                                                                       ##STR133##       SCH.sub.3                                         ##STR134## NH.sub.2          CH.sub.3                                         ______________________________________                                          ##STR135##                                                                    R.sup.1    R.sup.2     R.sup.3                                                 ______________________________________                                         CH.sub.3   Br          sec. C.sub.4 H.sub.9                                    CH.sub.3   Cl          tert. C.sub.4 H.sub.9                                   CH.sub.3   Cl                                                                                          ##STR136##                                             CH.sub.2CH.sub.2CH.sub.2                                                                           ##STR137##                                                 ______________________________________                                          ##STR138##                                                                    R.sup.1         R.sup.2                                                        ______________________________________                                         CH.sub.3        CH.sub.3                                                       CH.sub.3                                                                                        ##STR139##                                                     ##STR140##                                                                    ______________________________________                                          ##STR141##                                                                    R.sup.1   R.sup.2     R.sup.3                                                  ______________________________________                                          ##STR142##                                                                    sec. C.sub.4 H.sub.9                                                                     H                                                                     ##STR143##                                                                              tert. C.sub.4 H.sub.9                                                                      H                                                         ##STR144##                                                                              tert. C.sub.4 H.sub.9                                                                      CH.sub.3                                                 H         CH.sub.3    H        salts and esters                                H         sec. C.sub.4 H.sub.9                                                                       H        salts and esters                                H         tert. C.sub.4 H.sub.9                                                                      H        salts and esters                                H         tert . C.sub.4 H.sub.9                                                                     CH.sub.3 salts and esters                                ______________________________________                                          ##STR145##                                                                             R.sup.1                                                               ______________________________________                                                   ##STR146##                                                                     ##STR147##                                                                     ##STR148##                                                            ##STR149##                                                                    ______________________________________                                          ##STR150##                                                                    R.sup.1         X                                                              ______________________________________                                         H               CH.sub.3 OSO.sub.3                                             Br              CH.sub.3 OSO.sub.3                                             CH.sub.3        CH.sub.3 OSO.sub.3                                             CH.sub.3        CF.sub.3 SO.sub.3                                               ##STR151##                                                                     ##STR152##                                                                     ##STR153##                                                                     ##STR154##                                                                     ##STR155##                                                                     ##STR156##                                                                     ##STR157##                                                                     ##STR158##                                                                     ##STR159##                                                                    ______________________________________                                          ##STR160##                                                                    R.sup.1  R.sup.2    R.sup.3     R.sup.4                                        ______________________________________                                         H        Cl         NH.sub.2    Cl                                             H        I          I           I                                              Cl       H          Cl          OCH.sub.3                                      Cl       Cl         H           Cl                                             Cl       Cl         Cl          OCH.sub.3                                      ______________________________________                                          ##STR161##                                                                    R.sup.1     R.sup.2  R.sup.3                                                   ______________________________________                                          ##STR162## H        H       salts, esters, amides                              ##STR163## CH.sub.3 H       salts, esters, amides                              ##STR164## H        H       salts, esters, amides                              ##STR165## CH.sub.3 H       salts, esters, amides                              ##STR166## H        H       salts, esters, amides                              ##STR167## CH.sub.3 H       salts, esters, amides                              ##STR168##                                                                     ##STR169##                                                                     ##STR170##                                                                     ##STR171##                                                                     ##STR172##                                                                     ##STR173##                                                                     ##STR174##                                                                     ##STR175##                                                                     ##STR176##                                                                     ##STR177##                                                                     ##STR178##                                                                    R.sup.1                                                                        OH                                                                             CH.sub.3                                                                        ##STR179##                                                                     ##STR180##                                                                     ##STR181##                                                                     ##STR182##                                                                     ##STR183##                                                                     ##STR184##                                                                    ______________________________________                                    

It is also possible to apply the new compounds according to the invention, either alone or in combination with other herbicides, in admixture with other crop protection agents, e.g., agents for combatting pests or phytopathogenic fungi or bacteria. Of further interest is the fact that the compounds according to the invention may be mixed with mineral salt solutions used to overcome nutritional or trace element deficiencies.

To ensure the herbicidal action sets in, spreader-stickers and non-phytotoxic oils may be added.

Application may be effected for instance in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oi dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used; in any case they should ensure a fine distribution of the active ingredient.

For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, etc. and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.

Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sufonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated fatty alcohol glycol ether, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenol polyglycol ethers, alkylaryl polyester alcohols, isotridecyl alcohols, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.

Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.

The formulations contain from 0.1 to 95, and preferably 0.5 to 90, % by weight of active ingredient.

EXAMPLE 4

90 parts by weight of compound 2 is mixed with 10 parts by weight of N-methyl-α-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

EXAMPLE 5

20 parts by weight of compound 8 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 6

20 parts by weight of compound 13 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide to 1 mole of isoctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 7

20 parts by weight of compound 23 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210° and 280° C., and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 8

20 parts by weight of compound 7 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the sodium salt of a ligninsulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquid is obtained containing 0.1% by weight of the active ingredient.

EXAMPLE 9

3 parts by weight of compound 46 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.

EXAMPLE 10

30 parts by weight of compound 2 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

EXAMPLE 11

40 parts by weight of compound 7 is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. Dilution in 100,000 parts by weight of water gives an aqueous dispersion containing 0.04 wt% of active ingredient.

EXAMPLE 12

20 parts of compound 8 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.

                                      Table 1                                      __________________________________________________________________________     List of test plants                                                            Botanical term                                                                              Abbreviation in tables                                                                    Common name                                            __________________________________________________________________________     Amaranthus retroflexus                                                                      Amar. ret. redroot pigweed                                        Apium graveolens                                                                            Apium grav.                                                                               celery                                                 Arachis hypogaea                                                                            Arach. hyp.                                                                               peanuts (groundnuts)                                   Carthamus tinctorius                                                                        Carth. tinct.                                                                             safflower                                              Centaurea cyanus                                                                            Cent. cyan.                                                                               cornflower                                             Daucus carota                                                                               Daucus carot.                                                                             carrots                                                Datura stramonium                                                                           Datura stram.                                                                             Jimsonweed                                             Desmodium tortuosum                                                                         Desmod. tort.                                                                             Florida beggarweed                                     Euphorbia helioscopia                                                                       Euphorb. heliosc.                                                                         wart weed                                              Ruphorbia geniculata                                                                        Euphorb. genic.                                                                           South American member of the                                                   spurge family                                          Glycine max  Glyc. max  soybeans                                               Lamium spp.  Lamium spp.                                                                               dead-nettle                                            Matricaria spp.                                                                             Matric. spp.                                                                              chamomile                                              Mercurialis annua                                                                           Mercur. annua                                                                             annual mercury                                         Sesbania exaltata                                                                           Sesb. exalt.                                                                              hemp sesbania (coffeeweed)                             Setaria spp. Setaria spp.                                                                              foxtail spp.                                           Sinapis alba Sinap. alba                                                                               white mustard                                          Stellaria media                                                                             Stell. media                                                                              chickweed                                              Solanium nigrum                                                                             Solan. nigr.                                                                              black nightshade                                       Triticum aestivum                                                                           Tritic. aest.                                                                             wheat                                                  Xanthium pensylvanicum                                                                      Xanth. pens.                                                                              common cocklebur                                       Zea mays     Zea mays   Indian corn                                            Beta vulgaris                                                                               Beta vulg. sugarbeets                                             Chrysanthemum segetum                                                                       Chrys. seg.                                                                               corn marigold                                          Chenopodium album                                                                           Chen. alb. lambsquarters (goosefoot)                              Echinochloa crus galli                                                                      Echin. c. g.                                                                              barnyard grass                                         Gossypium hirsutum                                                                          Gossyp. hirs.                                                                             cotton                                                 Ipomoea spp. Ipom. spp. morningglory                                           Oryza sativa Oryza sat. rice                                                   Polygonum persicaria                                                                        Polyg. pers.                                                                              ladysthumb                                             __________________________________________________________________________

                                      Table 2                                      __________________________________________________________________________     Selective action in vegetable crops; postemergence application in the          greenhouse                                                                                                     Test plants and % damage                       Compound                    Apium                                                                              Daucus                                                                             Euphorbia                                                                            Datura                                                                             Lamium                           no.                     kg/ha                                                                              grav.                                                                              carota                                                                             heliosc.                                                                             stram.                                                                             spp.                             __________________________________________________________________________     1                       1.0  0   0  100   100 100.sup.+                                                2.0  0   10 100   100 100                                                      4.0  0   20 --    --  --                               4                       1.0  0   0   75   100  13                                                      2.0  0   0   80    90  53                                                      4.0 10   0  --    --  100                               ##STR185##             1.0 2.0 4.0                                                                        60 90 90                                                                           100 100 100                                                                         0  10 --                                                                            100 100 --                                                                          30 85 --                         ##STR186##             1.0 2.0 4.0                                                                         0 10 20                                                                           100 100 100                                                                        100 100 --                                                                           100 100 --                                                                         100 100 --                       __________________________________________________________________________      0 = no damage                                                                  100 = complete destruction                                                     .sup.+ Setaria spp. 92                                                   

                                      Table 3                                      __________________________________________________________________________     Selective herbicidal action of new compounds in cereals and                    Indian corn; postemergence treatment in the greenhouse                                                   Test plants and % damage                             Compound                  Tritic.                                                                            Zea                                                                               Cent.                                                                              Datura                                                                             Lamium                                                                               Matric.                                                                           Mercur.                                                                             Sinap.                                                                             Stell.              no.                   kg/ha                                                                              aest.                                                                              mays                                                                              cyan.                                                                              stram.                                                                             prup.                                                                               spp.                                                                               annua                                                                               alba                                                                               media               __________________________________________________________________________     90                    0.5  0   5  -- 100 100  100  75  92  98                                        1.0  0  15  -- 100 100  100  75  92  98                                        2.0  0  25  90 100 100  100  80  95  98                  98                    0.5  0  10  -- 100 100   50  50  90  95                                        1.0  0  20  --  -- 100   50  50  90  95                                        2.0  0  30 100  -- 100   50  95  95  95                  96                    2.0  0  --  50  -- 100   -- 100  90  --                   ##STR187##           0.5 1.0 2.0                                                                         0  6 10                                                                           30 30 40                                                                           85 100 100 100                                                                        100 100 100                                                                          63 63 63                                                                           47 67 77                                                                           95 97 99                                                                           98 98 98            prior art                                                                      __________________________________________________________________________      0 = no damage                                                                  100 = complete destruction                                               

                                      Table 4                                      __________________________________________________________________________     Action of new compounds in removal of weeds from oilseeds; postemergence       treatment in the greenhouse                                                                             Test plants and % damage                              Compound                 Arach.                                                                             Carth.                                                                              Glyc.                                                                             Amar.                                                                              Desmod.                                                                             Euphorb.                                                                            Sesb.                                                                             Solan.                                                                             Xanth.               no.                  kg/ha                                                                              hyp.                                                                               tinct.                                                                             max ret.                                                                               tort.                                                                               genic.                                                                              exal.                                                                             nigr.                                                                              pens.                __________________________________________________________________________      1                   0.5  0  --   4   88  98   57   97                                                                                50 100                                       1.0  0  0    7   90  98   57   98                                                                                60 100                                       2.0  5  0   11   98 100   67  100                                                                                60 100                   98                  0.5  0  --   0  100 100   90  100                                                                                50 100                                       1.0  0  0   15  100 100   95  100                                                                                70 100                                       2.0 10  0   30  100 100   95  100                                                                               100 100                  105                  0.5  0  --   0  100  10  100  100                                                                               100  40                                       1.0  0  0    0  100  30  100  100                                                                               100  40                  2.0                  10   0  0   100 100 100  100  100                                                                                40                       8                   0.5  0  --   0  100  10   50  100                                                                                40  30                                       1.0  0  0    0  100  10  100  100                                                                                50  30                                       2.0  0  0   10  100  60  100  100                                                                                50  30                  107                  2.0  0  0   20  100  20   90  100                                                                                60  40                   ##STR188##          0.5 1.0 2.0                                                                         0 10 10                                                                           -- -- --                                                                           30 30 35                                                                            50 60 60                                                                          100 100 100                                                                         100 100 100                                                                         100 100 100                                                                        40 60 60                                                                           30 100              __________________________________________________________________________                                                               100                   0 = no damage                                                                  100 =  complete destruction                                              

                                      Table 5                                      __________________________________________________________________________     Selective weed control in cereals; postemergence treatment in the              greenhouse                                                                                                  Test plants and % damage                          Compound                     Triticum                                                                            Mercurialis                                                                          Sinapis                                                                            Stellaria                          no.                      kg/ha                                                                              aestivum                                                                            annua alba                                                                               media                              __________________________________________________________________________      9                       1.0 --   100   100 100                                                         2.0  0   100   100 100                                 14                      1.0 --    --   100 100                                                         2.0  0    --   100 100                                 17                      1.0 --   100   100 100                                                         2.0  0   100   100 100                                 37                      1.0 --    0    100 100                                                         2.0  0    0    100 100                                 35                      1.0 --    0    100 100                                                         2.0  0    0    100 100                                 39                      1.0 --    0    100 100                                                         2.0  0    80   100 100                                 45                      1.0 --    40    70 100                                                         2.0  0    80    90 100                                 85                      1.0 --   100   100 100                                                         2.0  0   100   100  --                                 ##STR189##              2.0 20   100   100 100                                prior art                                                                       ##STR190##              1.0 2.0                                                                            82 92                                                                                -- --                                                                               100 100                                                                             -- --                             prior art                                                                       ##STR191##              1.0 2.0                                                                             0 0  38 55                                                                               100 100                                                                            100 100                            prior art                                                                       32                      2.0  0    --   100 100                                225                      2.0 30    70   100 100                                206                      0.5 --   100   100 100                                                         2.0  0   100   100 100                                231                      0.5 --    70   100 100                                                         2.0  0   100   100 100                                233                      0.5 --    --   100 100                                                         2.0  0    --   100 100                                144                      0.5  0   100    -- 100                                                         2.0  0   100    -- 100                                241                      0.5  0   100    -- 100                                                         2.0  0   100    -- 100                                217                      0.5  0    30    70  --                                                         2.0  0   100    95  --                                __________________________________________________________________________      0 = no damage                                                                  100 = complete destruction                                               

                                      Table 6                                      __________________________________________________________________________     Action on broadleaved weeds in groundnuts; postmergence treatment in the       greenhouse                                                                                                    Test plants and % damage                        Compound                       Arachys                                                                              Amaranthus                                                                            Desmodium                                                                             Sesbania                                                                             Xanthium              no.                       kg/ha                                                                               hypog.                                                                               retro. tort.  exalt.                                                                               pensyl.               __________________________________________________________________________     90                        0.5  5     100    100    100   50                                              2.0  20    100    100    100   50                    103                       0.5  0     100    90     95    50                                              2.0  0     100    90     95    50                    9                         0.5  10    100    90     95    80                                              2.0  10    100    90     95    90                    14                        0.5  0      20    20     80     0                                              2.0  0      50    90     95    20                    17                        0.5  0      10    90     85     0                                              2.0  0      30    90     85    25                     ##STR192##               0.5 2.0                                                                             0 10   0  40  0  0    0 20                                                                               60 100                 ##STR193##               0.5 2.0                                                                             0 0    0  0  100 100                                                                               100 100                                                                               0 20                 __________________________________________________________________________      0 = no damage                                                                  100 = complete destruction                                               

                  Table 7                                                          ______________________________________                                         Action of new compounds;                                                       postemergence treatment in the greenhouse                                                Test plants and % damage                                             Compound                                                                               kg/ha   Centurea   Lamium Sinapis                                                                              Stellaria                              no.     a.S.    cyanus     spp.   alba  media                                  ______________________________________                                         61      2.0     100        100    100   100                                    53      2.0     100        100    100   100                                    58      2.0     100        100    100   100                                    214     1.0     90         --     100   100                                    239     1.0     45         --     100   100                                    80      1.0     90         --     100   100                                    237     0.5     85         --      95   100                                    236     0.5     95         --      95   100                                    211     1.0     85         --     100   100                                    210     2.0     55         --      70   100                                    216     2.0     90         --      95   100                                    212     1.0     55         --     100   100                                    ______________________________________                                          0 = no damage                                                                  100 = complete destruction                                               

                                      Table 8                                      __________________________________________________________________________     New compounds having a selective herbicidal action in groundnuts;              postemergence treatment in the greenhouse                                                Test plants and % damage                                             Compound  Arach.                                                                             Amar.                                                                              Datura                                                                             Desmod.                                                                             Echin.                                                                             Ipom.                                                                              Sesb.                                                                              Solan.                                                                             Xanth.                              no.   kg/ha                                                                              hyp.                                                                               ret.                                                                               stram.                                                                             spp. c.g.                                                                               spp.                                                                               exalt.                                                                             nigr.                                                                              pens.                               __________________________________________________________________________      59   0.5 0   100 100 --   80  50  100 100 40                                        2.0 0   100 100 --   80  100 100 100 100                                 199   0.5 0    95  10 100  30  20  100 100 20                                        2.0 5   100  20 100  30  60  100 100 20                                  149   0.5 0   100  40 --   30   0  100 100 10                                        2.0 0   100 100 --   40  100 100 100 30                                  213   0.5 0   100 100 --   40  40  100 100 100                                       2.0 0   100 100 --   60  80  100 100 100                                 181   0.5 0   100 100 --   10  80    90                                                                               100 20                                        2.0 0   100 100 --   40  100 100 100 20                                  132   0.5 0   100 100 --   60  10  100 100 100                                       2.0 0   100 100 --   60  40  100 100 100                                 209   0.5 0    45 100 --   50  20  100 100 40                                        2.0 15  100 100 --   50  40  100 100 40                                   67    0.25                                                                              0    18 --   25  --  --  100  28 --                                        2.0 0   100 --  100  --  --  100  65 --                                  150   1.0 0   70  --  100  --  60  --  --  80                                  __________________________________________________________________________      0 = no damage                                                                  100 = complete destruction                                               

                                      Table 9                                      __________________________________________________________________________     New compounds having a selective herbicidal action in cereals and              Indian corn; postemergence treatment in the greenhouse                                   Test plants and % damage                                             Compound  Tritic.                                                                            Zea                                                                               Amar.                                                                              Cent.                                                                              Chrys.                                                                             Lamium                                                                              Matric.                                                                            Sinapis                                                                            Solan.                               no.   kg/ha                                                                              aest.                                                                              mays                                                                              ret.                                                                               cyan.                                                                              seg.                                                                               spp. spp.                                                                               alba                                                                               nigr.                                __________________________________________________________________________     218   0.5 0   0  100 100 100 100  90   95 100                                        1.0 0   0  100 100 100 100  100 100 100                                  201   0.5 0   0  100 100 100 100  50   90 100                                        1.0 0   10 100 100 100 100  100  95 100                                  118   0.5 0   0  100  30 --   70  40  100  10                                        2.0 0   0  100  60 --  100  60  100  30                                  187   0.5 0   0  100  60 --  100  40  100  70                                        2.0 20  10 100  60 --  100  60  100 100                                  115   2.0 0   0   73 --   93  70  --  100  60                                  __________________________________________________________________________      0 = no damage                                                                  100 = complete destruction                                               

                                      Table 10                                     __________________________________________________________________________     New compounds having a selective herbicidal action in cotton and               sugarbeets; postemergence treatment in the greenhouse                                                      Test plants and % damage                           Compound                    Beta                                                                              Gossyp.                                                                             Amar.                                                                              Datura                                                                             Lamium                                                                              Solan.                        no.                     kg/ha                                                                              vulg.                                                                             hirs.                                                                               ret.                                                                               stram.                                                                             spp. nigr.                         __________________________________________________________________________     240                     0.25                                                                               0   0   100 100 100  100                                                   2.0 0   5   100 100 100  100                            ##STR194##             0.25 2.0                                                                           0 2                                                                               27 78                                                                                6  16                                                                              82 100                                                                            100 100                                                                              46 92                          prior art                                                                    __________________________________________________________________________      0 = no damage                                                                  100 = complete destruction                                               

                                      Table 11                                     __________________________________________________________________________     Compounds having a selective herbicidal action in                              Indian corn and soybeans; postemergence treatment in                           the greenhouse                                                                           Test plants and % damage                                             Compound  Glyc.                                                                              Zea                                                                               Amar.                                                                              Chenop.                                                                             Desmod.                                                                             Ipomoea                                                                             Lamium                                                                              Mercur.                                                                             Setaria                          no.   kg/ha                                                                              max mays                                                                              ret.                                                                               album                                                                               tort.                                                                               spp. spp. annua                                                                               spp.                             __________________________________________________________________________      70   0.5 0   0  100 100  100  80   100  70   55                                     2.0 10  10 100 100  100  90   100  100  70                               151   0.25                                                                               0   0   30 100  --   70   100  60   70                                     2.0 0   5  100 100  100  95   100  100  85                               176   0.25                                                                               0   0  100 100  --   20   95   50   --                                     2.0 0   0  100 100  100  90   100  100  --                               __________________________________________________________________________      0 = no damage                                                                  100 = complete destruction                                               

                                      Table 12                                     __________________________________________________________________________     Compounds having a selective herbicidal action in cotton, groundnuts and       rice;                                                                          postemergence treatment in the greenhouse                                                Test plants and % damage                                             Compound  Arachys                                                                             Gossyp.                                                                             Oryza                                                                              Amar.                                                                              Datura                                                                             Lamium                                                                              Polyg.                                                                             Solan.                                no.   kg/ha                                                                              hyp  hirs.                                                                               sat.                                                                               ret.                                                                               stram.                                                                             spp. pers.                                                                              nigr.                                 __________________________________________________________________________     207   0.25                                                                               0    0    10   70 100  70  100 100                                         1.0 0    0    10  100 100 100  100 100                                         2.0 0    10   10  100 100 100  100 100                                   250   1.0 0    5    5    45 100 100   80 100                                         2.0 0    5    5   100 100 100   90 100                                   223   0.25                                                                               10   10   0    45  75 100   70 100                                         1.0 10   20   0   100 100 100  100 100                                   __________________________________________________________________________      0 = no damage                                                                  100 = complete destruction                                                

We claim:
 1. A diurethane of the formula ##STR195## where Z denotes the radical ##STR196## and Y denotes the radical ##STR197## Z always being different from Y and R¹ and R² being identical or different and each denoting hydrogen, alkyl selected from the group consisting of methyl, ethyl and isopropyl, alkoxyalkyl selected from the group consisting of methoxymethyl and 2-methoxyethyl, methoxycarbonylmethyl, and chloromethyl, R³ and R⁴ being identical or different and each denoting methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, 2-ethylhexyl or n-decyl, 2-chloroethyl, 2-methoxyethyl, methoxycarbonyl methyl or lower alkyl substituted by phenyl or substituted aryl, the aryl substituent selected from the group consisting of 4-chlorophenyl and 2,4-dichlorophenyl, unsubstituted or halogen-substituted alkenyl selected from the group consisting of allyl, 2-chloropropen-(1)-yl-(3), butene-(1)-yl-(3), 2,3-dichloroallyl and 3,3-dichloro-2-methylallyl, unsubstituted or halogen- or alkoxy-substituted lower alkynyl, unsubstituted or alkyl-substituted cycloalkyl selected from the group consisting of cyclopentyl, 1-methylcyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,6-dimethylcyclohexyl, cycloheptyl, 4-tert-butylcyclohexyl, cyclooctyl, cyclododecyl and 3,5-dimethylcyclohexyl, 3,3,5-trimethylcyclohexyl, norbornyl, adamantyl, tricyclo-(4,3,1²,5,0¹,6)-decyl, phenyl substituted with a fused ring system selected from the group consisting of naphthyl and indyl, phenyl or mono-or polysubstituted phenyl with the substituents lower alkyl, lower haloalkyl, lower alkoxyalkyl, lower alkoxycarbonylalkyl, cycloalkyl having 5 or 6 ring members, halogen, alkoxy, lower haloalkoxy, lower alkoxycarbonylalkoxy, nitro, amino, phenyl, phenoxy, thiocyanato, cyano ##STR198## R⁵ and R⁶ being identical or different and each denoting hydrogen, or phenyl and A, B, D and E being identical or different and each denoting oxygen or sulfur (with the proviso that one of these always denotes sulfur), X denotes hydrogen, lower alkyl, lower haloalkyl, lower alkoxy, halogen, nitro or amino, and n denotes one of the integers 1, 2, 3 and
 4. 2. A process for combatting the growth of unwanted plants by treatment with a diurethane of the formula ##STR199## where Z denotes the radical ##STR200## and Y denotes the radical ##STR201## Z always being different from Y and R¹ and R² being identical or different and each denoting hydrogen, alkyl selected from the group consisting of methyl, ethyl and isopropyl, alkoxyalkyl selected from the group consisting of methoxymethyl and 2-methoxyethyl, methoxycarbonylmethyl, and chloromethyl, R³ and R⁴ being identical or different and each denoting methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, 2-ethylhexyl or n-decyl, 2-chloroethyl, 2-methoxyethyl, methoxycarbonylmethyl or alkyl substituted by phenyl or substituted aryl, the aryl substituent selected from the group consisting of 4-chlorophenyl and 2,4-dichlorophenyl, unsubstituted or halogen-substituted alkenyl selected from the group consisting of allyl, 2-chloropropen-(1)-yl-(3), butene-(1)-yl-(3), 2,3-dichloroallyl and 3,3-dichloro-2-methylallyl, unsubstituted or halogen- or alkoxy-substituted lower alkynyl, unsubstituted or alkyl-substituted cycloalkyl selected from the group consisting of cyclopentyl, 1-methylcyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,6-dimethylcyclohexyl, cycloheptyl, 4-tert-butylcyclohexyl, cyclooctyl, cyclododecyl and 3,5-dimethylcyclohexyl, 3,3,5-trimethylcyclohexyl, norbornyl, adamantyl, tricyclo-(4,3,1²,5,0¹,6)-decyl, phenyl substituted with a fused ring system selected from the group consisting of naphthyl and indyl, phenyl or mono- or polysubstituted phenyl with the substituents lower alkyl, lower haloalkyl, lower alkoxyalkyl, lower alkoxycarbonylalkyl, cycloalkyl having 5 or 6 ring members, halogen, lower alkoxy, lower haloalkoxy, lower alkoxycarbonylalkoxy, nitro, amino, aryl, lower aryloxy, thiocyanato, cyano, ##STR202## R⁵ and R⁶ being identical or different and each denotinhg hydrogen, or phenyl and A, B, D and E being identical or different and each denoting oxygen or sulfur (with the proviso that one of these always denotes sulfur), X denotes hydrogen, lower alkyl, lower haloalkyl, lower alkoxy, halogen, nitro or amino, and n denotes one of the integers 1, 2, 3 and
 4. 3. A diurethane selected from the group consisting of the compounds of the formulae ##STR203##
 4. A diurethane according to claim 1 in which at least one of said R³ and R⁴ is alkyl substituted by a halo or alkyl substituted aryl.
 5. A diurethane according to claim 1 in which at least one or R³ and R⁴ is 2,4-dihalobenzyl or 2-phenylalkyl.
 6. A process for combatting the growth of unwanted plants according to claim 2 in which at least one of R³ and R⁴ is alkyl substituted by a halo or alkyl substituted aryl.
 7. A process for combatting the growth of unwanted plants according to claim 2 in which at least one of R³ and R⁴ is 2,4-dihalobenzyl or 2-phenylalkyl.
 8. A diurethane according to claim 1, wherein R¹ and R² are identical or different and each denotes hydrogen, alkyl selected from the group consisting of methyl, ethyl and isopropyl, alkoxyalkyl selected from the group consisting of methoxymethyl and 2-methoxyethyl, methoxycarbonylmethyl, and chloromethyl, and R³ and R⁴ are identical or different and each denotes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, 2-ethylhexyl or n-decyl, 2-chloroethyl, lower alkyl substituted by phenyl or substituted aryl, the aryl substituent selected from the group consisting of 4-chlorophenyl and 2,4-dichlorophenyl, unsubstituted or halogen-substituted alkenyl selected from the group consisting of allyl, 2-chloropropen-(1)-yl-(3), butene-(1)-yl-(3), 2,3-dichloroallyl and 3,3-dichloro-2-methylallyl, unsubstituted or halogen-substituted lower alkynyl, unsubstituted or alkyl-substituted cycloalkyl selected from the group consisting of cyclopentyl, 1-methylcyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,6-dimethylcyclohexyl, cycloheptyl, 4-tert-butylcyclohexyl, cyclooctyl, cyclododecyl and 3,5-dimethylcyclohexyl, 3,3,5-trimethylcyclohexyl, norbornyl, adamantyl, tricyclo-(4,3,1²,5,0¹,6)-decyl, phenyl substituted with a fused ring system selected from the group consisting of naphthyl or indyl, or phenyl or or mono- or polysubstituted phenyl with the substituents halogen, nitro, amino, thiocyanato, cyano, ##STR204## R⁵ and R⁶ being identical or different and each denoting hydrogen, or phenyl and A, B, D and E being identical or different and each denoting oxygen or sulfur (with the proviso that one of these always denotes sulfur), X denotes hydrogen, lower alkyl, lower haloalkyl, lower alkoxy, halogen, nitro or amino, and n denotes one of the integers 1, 2, 3 and
 4. 9. A process for combatting the growth of unwanted plants by treating them with a diurethane according to claim
 8. 